Spain will need Rafael Nadal to be on song on Sunday after they fell 2-1 behind to Germany in their Davis Cup quarter-final, while France and Croatia are also set for the last four.
Feliciano López and Marc López fought gallantly after losing the first two sets, drawing level in a marathon match of over four-and-a-half hours, but Tim Puetz and Jan-Lennard Struff eventually sealed a shock 6-3 6-4 3-6 6-7 (4-7) 7-5 victory.
Now world number one Nadal must beat world number four Alexander Zverev if Spain are to avoid defeat in the last eight. David Ferrer and Phillip Kohlschreiber will play the decisive rubber if it goes to the wire in Valencia.
France open up 2-1 lead over Italy
The other two European match-ups are also 2-1 as it stands. The French doubles team - boasting the ATP's ninth-ranked doubles player Nicolas Mahut alongside Pierre Hugues Herbert - raced to victory in straight sets, defeating Italy 6-4 6-3 6-1.
Fabio Fognini and Simone Bolelli were swiftly seen off, fading after holding their own early on and the former - ranked 20th - will have to beat 11th-ranked Lucas Pouille to keep Italy in the competition.
Croatia's Ivan Dodig and Nikola Mektic came from behind to beat Timur Khabibulin and Aleksandr Nedovyesov of Kazakhstan 6-7 (2-7) 6-4 6-4 6-2.