Barcelona can clinch their 19th La Liga title on Sunday after nearest rivals Real Madrid lost 2-0 to Valencia on Saturday evening.
On the back of Barca's emphatic 6-2 success over Real last weekend they can now clinch their first title since the 2005/06 campaign with victory over Villarreal.
Juande Ramos' Real Madrid were always on the back foot at the Mestalla and the only surprise of the game was it took 29 minutes for Valencia to break the deadlock.
Iker Casillas had already made one world-class save to deny Ruben Baraja, but was helpless to prevent Juan Mata finding the back of the net after he got the better of Fabio Cannavaro.
One soon became two when David Silva's speculative shot squirmed past Casillas on 32 minutes at his near post to double Valencia's lead.
Los Che ensured there would be no comeback from Real when Baraja showed superb technique when lashing a left-footed volley past the helpless Casillas on 68 minutes.
Real remain seven points adrift of the leaders Barca, who can move an unassailable 10 points clear of their rivals on Sunday with three league games remaining.
Elsewhere, Sevilla battled back from a goal down to see off Real Mallorca while Real Betis remain in relegation trouble after losing at Athletic Bilbao.
Real Mallorca stunned Sevilla when they took the lead at Estadio Ramon Sanchez when Aritz Aduriz scored from the angle on 16 minutes.
However, parity was restored when Fredi Kanoute sent Miguel Moya the wrong way from the penalty spot after Luis Fabiano was felled.
The Brazilian marksman put Sevilla ahead for the first time in the game on the hour mark with a superb individual run that led to a neat finish.
The home side wrapped up the points late on when Jesus Navas cut in from the right wing before lashing an unstoppable drive past Moya.
Elsewhere, Real Betis remain just three points clear of third from bottom Sporting Gijon following a 1-0 defeat at Athletic Bilbao.
Inigo Velez scored the only goal of the game on 28 minutes to move Bilbao within a point of Mallorca in the Liga table.
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