Julian Alaphilippe ended Alejandro Valverde's dominance of La Fleche Wallonne by becoming the first Frenchman to win the race for 21 years.
Valverde had been crowned champion in each of the last four years, but the Spaniard was runner-up to Quick-Step Floors rider Alaphilippe in the hilly Belgian Classic on Wednesday.
Alaphilippe had enough in the tank to move away from Valverde on the final climb of the Mur de Huy and the Movistar man had to settle for second spot, finishing four seconds behind the 25-year-old.
Jelle Vanendert (Lotto Soudal) was third ahead of Mitchelton-Scott's Roman Kreuziger and Michael Matthews of Team Sunweb at the end of the 198.5-kilometre race, which started in Seraing.
Vincenzo Nibali (Bahrain-Merida) made a bold move with 46km to race after a group of eight - including birthday boys Anthony Roux and Patrick Muller - had been reeled in.
Mikel Landa helped to keep Valverde in the hunt to win it for a sixth time and it was Jack Haig (Mitchelton-Scott) and Maximilian Schachmann (Quick-Step Floors) who were the last men standing at the front when Nibali was caught at the foot of the Mur.
Vanendert powered his way past Schachmann with around 150m to go, but Alaphilippe stuck to his wheel and moved into the lead with a strong burst.
Valverde reacted, but another kick from Alaphilippe proved to be decisive as the long-time champion was finally dethroned.
1. Julian Alaphilippe (Quick-Step Floors) 4:53.37
2. Alejandro Valverde (Movistar) +0.04
3. Jelle Vanendert (Lotto Soudal) +0.06
4. Roman Kreuziger (Mitchelton-Scott) +0.06
5. Michael Matthews (Team Sunweb) +0.06
6. Bauke Mollema (Trek-Segafredo) +0.06
7. Tim Wellens (Lotto Soudal) +0.06
8. Maximilian Schachmann (Quick-Step Floors) +0.06
9. Romain Bardet (AG2R La Mondiale) +0.06
10. Patrick Konrad (Bora-Hansgrohe) +0.12