Sevilla heaped more misery on Real Madrid with a 1-0 win, while rivals Barcelona continued their perfect start to the La Liga season.
Defending champions Real were already five points adrift of league leaders Barcelona heading into Saturday s match after drawing and losing two of their opening three matches.
And that gap extended to eight points following Piotr Trochowski s goal in just the second minute of play.
The match started at a frenetic pace with the hosts taking the game up to Jose Mourinho s men.
A shot from the edge of the box inside the first minute was spilled back into the danger area by Iker Casillas but he recovered to stop Alvaro Negredo from tapping in the rebound.
Former Schalke midfielder Ivan Rakitic took the resultant corner where it was met by Trochowski, who had escaped the loose marking of Angel Di Maria and volleyed into the roof of the net.
In search of an equaliser, Real hit the post twice but could not prevent Sevilla from claiming their first win against the Spanish champions since October 2009.
Barcelona maintained their 100 percent start to the season with a 4-1 triumph against Getafe at the Coliseum Alfonso Perez.
Tito Vilanova s side laboured during the early stages of the match but took a single-goal lead into the break through Adriano.
Second-half substitute and two-time Ballon d Or winner Lionel Messi then netted twice before a Javier Mascherano own goal robbed the visitors of a clean sheet, but David Villa rounded off the win in the closing moments.
Though the result may have been somewhat flattering, Barcelona moved back to the summit with a two-point advantage over their nearest rivals Malaga, who maintained their unbeaten start to the season at home to Levante.
Malaga, the surprise packets of this season s competition, ran out 3-1 winners thanks to goals from Javier Saviola, Joaquin and Francisco Portillo.
Meanwhile, Valencia ended their winless start to the 2012/13 campaign with a 2-1 victory over Celta de Vigo at the Estadio de Mestalla.
Valencia broke the deadlock through Sofiane Feghouli in the fourth minute before Michael Krohn-Dehli restored parity on 16 minutes.
However, the hosts restored their one-goal advantage five minutes into the second half after Aly Cissokho s headed home Tino Costa s cross.
