Barcelona dropped points at home for the first time this season as Valencia snatched a last-gasp win at home to Espanyol.
Reigning Primera Liga champions Barcelona were held to a 1-1 draw as Villarreal ended their 100 per cent record at Camp Nou this season.
The recently crowned world club champions enjoyed a dream start by taking the lead on seven minutes through Pedrito after Thierry Henry had been denied by the crossbar.
However, Villarreal earned a point early in the second half when David Fuster converted Cani's cross to leave Barca three points ahead of closest pursuers Real Madrid.
Valencia moved up to third spot in the table after substitute Nikola Zigic scored an injury-time winner against Espanyol.
David Villa had been thwarted by the woodwork on 77 minutes before Zigic rose well in the third minute of stoppage-time to glance Joaquin's cross inside the far post.
Antonio Lopez headed home deep into stoppage-time as Atletico Madrid came from behind to beat 10-man Sevilla 2-1 at home.
Sevilla, who were looking to reclaim third spot from Valencia, took a 44th minute lead when Renato headed home Diego Perotti's corner.
Ivica Dragutinovic's own goal drew Atletico level three minutes into the second half before Sevilla midfielder Aldo Duscher was sent off for a second bookable offence on 72 minutes.
And in the fourth minute of added time, Atletico nicked the points when Lopez was left unmarked to head Simao's free-kick inside the upright.
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