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 Lopez and Marc Lopez 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.
The other two European match-ups are also 2-1 as it stands, as the French pair - 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.
