Barcelona were crowned Primera Division champions for the first time since 2006 after Real Madrid were beaten 3-2 at Villarreal tonight.
Madrid twice came from behind to draw level, but keeper Iker Casillas' error in stoppage time gifted Villarreal the victory which leaves Juande Ramos' men eight points behind Barca with just two games left.
Even a draw, though, would not have been enough for Madrid to stay in the title hunt.
Barcelona travel to Real Mallorca tomorrow, but the Catalans' focus can now turn to their Champions League final meeting with Manchester United.
It is the second trophy for Barcelona this term after they secured the Copa del Rey in midweek.
Villarreal denied Pep Guardiola's men the title last weekend as they scored a last-gasp leveller at the Nou Camp, and there was another thrilling climax at El Madrigal, although this time Barca were the beneficiaries.
The normally unflappable Casillas dropped a cross at the feet of Joan Capdevila who tapped home the winner at the death.
Gonzalo Higuain had looked to have secured a point for Madrid with an 88th-minute leveller which looked clearly offside.
Earlier Robert Pires (17) and Ruben Cani (62) twice put the Yellow Submarine ahead either side of a Rafael Van der Vaart equaliser.
The win moved Villarreal level on points with Valencia in the race for fourth place and the final Champions League qualification spot. The two sides meet next weekend.
