Villarreal thrashed struggling Elche 4-0 in La Liga on Sunday to keep their unbeaten start intact and stay within two points of leaders Real Madrid.
Gerard Moreno and Giovani Lo Celso scored in the first half before Francis Coquelin and Jose Luis Morales struck in the closing minutes.
Unai Emery's side are the only team yet to concede a goal in the Spanish top flight and sit level on 10 points with Barcelona.
Athletic Bilbao's unbeaten run ended with a 1-0 home loss to Espanyol as Martin Braithwaite scored on his debut days after his contract with Barcelona was terminated.
Valencia hammered Getafe 5-1 with Gennaro Gattuso's team bouncing back from consecutive one-goal losses.
Osasuna won for the third time in four games courtesy of Ruben Garcia's late goal in a 2-1 victory over Rayo Vallecano.