Real Madrid missed the chance to extend their lead at the top of the table after losing 2-0 at Sevilla.
Sevilla stunned Madrid with two goals in as many minutes in the first-half to lay the platform for the victory.
Seydou Keita fired Sevilla in front on 19 minutes with a stunning shot from the edge of the box.
The home side doubled their lead two minutes later when Luis Fabiano scored from close-range after Iker Casillas had kept out Fredi Kanoute's initial shot.
Things got worse for Real in the second-half when former Sevilla star Sergio Ramos was sent off on 51 minutes for a second bookable offence.
Fabiano really should have added a third goal soon after when with only Casillas to beat he somehow lifted his shot over the crossbar.
Valencia climbed up to fourth spot with a 2-0 win over Real Mallorca courtesy of a Fernando Morientes brace.
Caretaker boss Oscar Fernandez took charge of Valencia as Ronald Koeman does not take charge until next week's UEFA Champions League tie with Rosenborg.
Morientes broke the deadlock right on the stroke of half-time when he converted Miguel's cross at the far post.
The former Liverpool striker added his second just past the hour mark when he scored from close-range after being picked out by David Silva.