A thrilling game at the Mestalla saw Barcelona come away with all three-points against Valencia thanks to a last-minute Lionel Messi penalty.
The home side had come from behind to lead 2-1 after the break, with well worked goals from on-loan Barcelona forward Munir and Rodrgio cancelling out Messi's first half strike.
Having turned the game on its head following a dominant display from the Catalan side in the opening 45 minutes, Valencia were unable to hold on to their lead, conceding almost immediately via a Luis Suarez goal on 61 minutes.
However Cesare Prandelli's side took the ascendancy again in the closing twenty minutes and pushed for a deserved winner. And it almost came through Nani who could only shoot wide when clean through with five minutes remaining.
Valencia would live to regret that missed opportunity when in the 92nd minute, Luis Suarez was hauled down and the referee pointed to the spot.
With the final kick of the game, Messi put just enough on his penalty to see it squirm past specialist spot-kick stopper, Diego Alves.
It was a cruel blow for Valencia who were left with nothing from their impressive display. Barcelona, meanwhile, go top of La Liga having played a game extra than rivals Real Madrid and Atletico, who both are in action on Sunday.
As it happened:
Full time: Valencia 2-3 Barcelona
96 mins | Ugly scenes as a water bottle is thrown from the crowd as Barça players celebrate. The bottle his the Barça huddle and both Suarez and Neymar fall to the ground, rather theatrically. They are alright though. The ref blows up and that was the last action. What drama!
95 mins | GOOOOOOOAL! Messi dispatches the pen and wins the game for Barcelona. It was a stonewall pen as Garay brought down Suarez. Alves -- the penalty saving king -- went the right way but Messi put just enough on it and it squirmed into the corner. Game over.
92 mins | Penalty Barcelona! Messi to take....
90 mins | 2 minutes added
90 mins | Valencia break and its 3 on 2! Santi Mina dribbles forward with options either side but his execution is poor and his pass to Munir slows things down, allowing Barça to recover and eventually dispossess. Chance gone!
88 mins | We're into the final few minutes. Will somebody prevail? Barça now the ones pushing forward in search of the winner....
86 mins | My prediction very almost comes true! The balls falls to Mangala from a corner (after he is manhandled by Mascherano) but the big defender loses his footing. That for a moment sat up nicely for him to blast in from six yards but he couldn't quite get there.
85 mins | This is not meant to be another commentators curse, but Valencia looking the more likely to go on and win this. Barcelona looking very tired.
82 mins | Nani!!!! Misses! Oh dear, that was a big, big chance and Nani fluffs his lines. Some very slack defending lets the former Man United man clean through on goal but he fires wide when at the very least he should have worked Ter Stegen. Could Valencia live to regret that?
79 mins | Valencia break and Mario Suarez receives it in the box. He still has a man in front of him to beat and options inside but he tries a stepover and proceeds to step on the ball like a wally. He loses the ball and Barça promptly clear.
75 mins | Yet another yellow! You'd say this ref is card happy, but this one really was deserved. Enzo takes out Neymar with a flying sliding tackle and gives away a free-kick in a danger zone. Just like Messi before him, Suarez blasts it over.
74 mins | Messi breaks into the box and he goes down under the challenge of Valencia captain Perez. His tackle is timed to perfection though and the chance is lost for Barça.
72 mins | The yellow cards and piling up. Messi is the latest to go into the book for complaining that he was wrongly penalised for a foul.
70 mins | Barca sub: Denis Suárez on for Gomes. Valencia sub: Rodrigo Moreno leaves the field, Santi Mina enters.
69 mins | Mario Suarez receives a yellow for bringing down Neymar. Messi blasts the resulting free kick high and wide from a decent position.
69 mins | Finally able to catch a breath after that frantic third quarter. The rhythm has slowed down considerably.
64 mins | What a second half this has been. Valencia really had their tales up after going in front. How will they react now to losing their lead?
61 mins | Suarez!!!! 2-2! I've only gone and commentator-cursed Valencia (see last post). Alves saves wonderfully from a Neymar header but the ball falls straight to Suarez and he does his best Rodrigo impression by blasting it as hard as he could into the net! We have a quite a game here!
58 mins | On the balance of play in the second half you wouldn't argue against this scoreline. Valencia have come out a different team and look like a side possessed! What on earth did Prandelli say to them at the interval!?
56 mins | GOOOOOOOAL Rodrigo! The game's been turned on its head. It's another beauty from Valencia. A delicious dinked ball over the top from Nani sees Rodrigo beat the offside trap and absolutely rifle it past Stegen on the half volley. Out of nowhere Valencia are in the lead!
52 mins | GOOOOOOAL! It's Munir, who's on loan from Barça! And it's a wonderful goal too. Parejo pulled it back and he guided it with the outside of his foot past Stegen from 20 yards. Munir, unsurprisingly, doesn't celebrate against his primary employers.
51 mins | Yellow card for Neymar for a cynical block on Munir.
50 mins | Rakitic simply has to score, but he hits the post! Neymar's shot was parried by Alves and Rakitic had all the time in the world to guide in the rebound...but he somehow misses the target.
47 mins | Yellow for Digne for a high elbow on Munir. That was Munir's first introduction to the game. He replaced Montoya at half time.
46 mins | Peeeeeeeep! We're back underway
Half time: Valencia 0-1 Barcelona
45 mins | Neymaaaaaaar.....no! The Brazilian set himself up for a bicycle kick with his back to goal and for a second it looks to be heading for the top comer. Replays show it went well wide however and that's that. Ref blows for HT.
44 mins | Chance Parejo! It's Ter Stegen to the rescue as against the run of play Parejo all of a sudden finds himself free in the box. His first touch is heavy though and the keeper rushes out to smother.
Valencia XI: Diego Alves, Montoya, Garay, Mangala, Gayá, Enzo Pérez, Mario Suárez, Cancelo, Parejo, Nani, Rodrigo
Barcelona XI: Ter Stegen; Sergi, Mascherano, Umtiti, Digne; Gomes, Busquets, Iniesta; Messi, Suarez, Neymar
Valencia vs Barcelona: latest news
16:12 | And here they come onto the pitch. Sit tight!
16:10 | Here we go. The players gather in the tunnel. It's all bum taps, hand slaps and serious faces. A crucial game for both sides at this stage of the season, you feel.
16:00 | Fifteen minutes to go! The Mestalla is filling to capacity and there's that unmistakable smell of optimism in the air that a new coach (in this case Cesare Prandelli) often brings to a club. He got off to a perfect start last week, could he continue that here against Barça? We'll soon find out.
15:52 | A reminder of how things stand in the La Liga table. Valencia lie in 15th, two points of the relegation zone. A win this afternoon could lift them, temporarily at least, all the way up to 9th. If Barça come away victorious, then they can put pressure on Real Madrid and Atleti (who both play tomorrow) by going top by one point.
15:50 | Both teams are now out on the pitch warming up, doing all those familiar fancy stretches and exercise drills.
15:45 | Half an hour warning! Just 30 minutes till kick-off guys, so slip into something comfortable, gather your snacks, and prepare to settle down for what could be the game of the century. Could be, you just never know, do you?
15:34 | The teams are out (see above) and as we knew already, there's no Pique or Alba for Barcelona so Digne and Sergi deputise in their absence. It's also a special moment for Andre Gomes as he's called up in place of Rakitic to face his old side. The only change for Valencia from their last outing is Nani coming in for Mina.
15:20 | Odds watch: Barcelona are favourites to win this afternoon's match, with most bookies placing them at 4/11. You can get Valencia at a best price of 13/2, and if you fancy a draw, 9/2.
15:12 | Don't forget it's not too late to look over our Week 9 La Liga predictions. We can smugly tell you that we got Saturday's first game spot on, as Espanyol drew with Eibar. We've got the Valencia-Barcelona match down as an away win, for the record.
14:39 | New Valencia coach Cesare Prandelli admitted yesterday that "there is no formula to stop Lionel Messi". I think most top coaches have learned that the hard way by now.
13:04 | Fancy some "individual moves" (see 10:19 update)? You can follow today's early game between Espanyol and Eibar.
12:21 | The weather in Valencia right now is a very nice 20° C, however there are some thunderstorms doing the rounds. These storms should have cleared for kick-off with 23°C a likely temp by 16:15.
11:11 | AS editor Alfredo Relaño wrote this morning about Barça and other Spanish clubs signing up their stars on longer and more lucrative contracts to deter the preying claws of the Premier League.
10:19 | *...not that there's anything wrong with "Messi does individual move".
10:18 | As you are more than accustomed to by now, AS English will be bringing you a chatty and insightful version of commentary* for the game. But for those of you who like to support this with some actual moving pictures, allow us to guide you.
Valencia vs Barca: match preview
Two historically huge teams of the Spanish league come together this afternoon for a clash that in the past has got the juices flowing. Today may not whet the appetite like those clashes at the start of this century but nonetheless there is plenty to cause interest and intrigue. And with Halloween approaching can the team with the bat on their crest cause an upset?
After an awful start to the 2016/17 campaign - which saw Los Ché lose their first four league games - confidence has started to return as new head coach Cesar Prandelli starts to get his message across to the playing staff. Wins against Alavés, Leganés and Sporting, all by two goals to one with two away from home, seem to have steadied the recently unsteady ship with a 0-2 defeat to top of the table between them not a particular embarrassment given the form of the Rojiblancos. Three points against last year's champions may be a tough ask, but the Italian coach will be looking for something positive to take into his next run of games and their potential climb up the table.
Prandelli will be looking to some of his key players to shine after some time out and make the difference tonight. With the skilfull Portuguese forward Nani at the club there is always the potential for some magic. Whether he gets to see enough of the ball is another thing. At the back Mangala and Garay will more than likely have their hands full but if they can frustrate the MSN, chances may present themselves at the other end. Mario Suárez with two in the last outing will be looking to capitalise.
Luis Enrique's men take the short trip south in very high spirits. Their 4-0 win was maybe a little flattering given the performance of Man City but was a convincing enough display of their credentials against a Pep Guardiola side that many have favourites to win the Premier League. Prior to the European match Barça had scored 18 goals in four league game - granted one of those games was the 4-3 loss to Celta - and several commentators have already stated that another rout today is on the cards.
As Messi's return to the side has provided some sparkling displays including that hat-trick on Wednesday night much of the attention will again be focused on the attacking threat offered by his partnership with Suárez and Neymar. Much further behind them, however, lesser seen faces will be brought in due to injuries to first choicers Piqué and Alba who were taken off midweek. Enrique will be looking for his midfield trio of Iniesta, Rakitic, Busquets to take control from the off in what will be a noisy Mestalla that may see the appearance of an old favourite.