Barcelona rose to second after they secured a comfortable 3-0 victory over Athletico Madrid thanks to goals from Deco (17), Lionel Messi (20) and Xavi (90).
Villarreal suffered their second defeat of the season after Osasuna claimed a 3-2 victory. Giuseppe Rossi (20) put the away side ahead but Osasuna replied through Juan Juanfran (21) and Eduardo Dady (34). Diego Godin (36) levelled for Valencia but Franciso Javi Garcia (79) scored late on to hand Jose Angel Ziganda's men all three points.
Sergio Garcia (64) scored Real Zaragoza's opener as they moved up to eighth with a 3-0 win over Levante. Ricardo Oliveira (70 and 82) put the result beyond doubt with a late brace.
Athletic Bilbao were held to a 1-1 draw against Almeria at the Estadio San Mames. Joseba Etxeberria (32) put the home side in front but Felipe Melo levelled with 28 minutes remaining.
Gregorio Manzano's Real Mallorca put on an inspired second half display to come back from two goals behind. Francisco Sousa (3 and 48) put Getafe ahead but Ariel Ibagaza (55), Juan Arango (72 and 79) and Ivan Ramis (93) sealed an impressive 4-2 win.
Sevilla lost their fourth consecutive league game following a 1-0 home defeat to Deportivo La Coruna. Riki got the goal for Deportivo with just 17 minutes remaining.
Elsewhere, Murcia and Real Betis shared the spoils following a 0-0 draw at La Condomina.