Villarreal will be in high spirits ahead of Wednesday's Champions League trip to Old Trafford to face reigning champions Manchester United after a 1-0 home victory over Deportivo La Coruna on Sunday.
It was a first win of the season for Villarreal, Champions League semi-finalists in 2006, who will hope to pile more misery on Man Utd after their 2-1 league loss at Liverpool.
Spanish international Santiago Cazorla, a target for Real Madrid during the transfer window, scored the decisive goal on 27 minutes with a fierce left-footed shot.
Depor had taken the scalp of Real Madrid on the opening weekend but were outclassed by Villarreal and only a combination of inspired goalkeeping and poor finishing kept them at bay.
A major boost for Villarreal was the return of Robert Pires after three weeks out through injury.
The veteran French midfielder came off the substitutes bench to play the final 23 minutes of the match.
Villarreal striker Giusepppe Rossi was again absent as he continues to struggle with an ankle injury and his chances of facing former club Manchester United look slim.
Villarreal climb to fourth and Espanyol are the new league leaders following a 1-0 win over Recreativo Huelva with Luis Garcia striking six minutes from time.
Espanyol, who fell apart in the second half of last season, are now the only team with a maximum six points although Valencia and Numancia have yet to play.
Real Betis handed a debut to Spanish international striker Sergio Garcia – a ten million euro signing from Real Zaragoza – but he could not find the back of the net as his side drew 0-0 at Getafe.
Athletic Bilbao and Malaga also shared the spoils in a scoreless draw.
Real Mallorca halved the points against Osasuna in a 1-1 draw with Javier Portillo, once touted as the next big thing at Real Madrid, equalising late on for Osasuna.
Later on Sunday reigning champions Real Madrid go in search of their first win against promoted Numancia at the Santiago Bernabeu.
Real will want to capitalise on Barca's poor start to the campaign – just one point from six – but coach Bernd Schuster is wary of the threat posed by Numancia.
“Promoted teams are always extra motivated at the start of the season because the first few points are crucial for them,” explained Schuster. “They will have nothing to lose against us.”
Valencia can secure a maximum six points from the opening two games when they travel to Almeria late on Sunday.
Valencia coach Unai Emery returns to his old club and Portuguese international Miguel hopes some inside knowledge can give Valencia the edge.
“Emery was Almeria coach and knows their players well and we can take a lot of good things from that,” said Miguel.
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