Nilmar's first half strike was enough to give Villarreal a narrow 1-0 victory at home to Deportivo La Coruna and saw the Yellow Submarine move into third place after four rounds of the season.
Nilmar's fourth goal of the season makes him the league's top scorer as Villarreal - having lost their opening match at Real Sociedad - go from strength to strength.
The Brazilian latched on to a ball from Angel and beat Manu with a venomous drive which went in off the post.
It is now three wins on the bounce for Juan Carlos Garrido4s side and with games against Malaga, Racing Santander and Hercules ahead in the coming weeks, they will be confident of building on their positive start.
Sevilla missed the chance to go top of the table after they were held to a 1-1 draw by Racing Santander at the Sanchez Pizjuan.
A win would have seen the Andalusian side move above Real Madrid and Valencia on goal difference. And it looked likely after Alvaro Negredo put them in front from the penalty spot after 13 minutes.
But Racing hit back nine minutes into the second half with an impressive goal from Pablo Pinillos and the Cantabrians could have gone on to take all three points as they dominated in the closing stages. It was anybody's game late on but the draw was just about fair in the end.
Malaga continue to enjoy life on the road after second-half goals from Jose Salomon Rondon and Antonio Apono gave them a deserved 2-0 victory over Getafe in a game which saw both teams finish with 10 men.
Malaga have lost both of their home games this season but have looked impressive on their travels, downing Real Zaragoza 5-3 a fortnight ago before their triumph over Getafe on a rainy night in Madrid.
Rondon opened the scoring in the 54th minute before Apono doubled the visitors' lead eight minutes later from the penalty spot in an incident that also saw Getafe defender Rafa Lopez sent off.
Malaga only enjoyed numerical superiority for four minutes before they too were reduced to 10 men, captain Jesus Gamez getting his marching orders, but despite Getafe pushing hard in the closing stages, the visitors were not to be denied.