Early strikes from Giuseppe Rossi and Joseba Llorente earned Villarreal a 2-1 home victory against Almeria, and Valencia saw off ten-man Getafe 3-0 away with goals from Manuel Fernandes, Joaquin and Vicente.
Barca are top with 25 points from ten games, one ahead of Villarreal, after hammering Valladolid 6-0 at the Nou Camp on Saturday.
Valencia have 23 points and moved above Real Madrid into third on goal difference. The champions scrambled a 4-3 comeback win at home to Malaga on Saturday.
Villarreal's Italian forward Rossi scored inside the first minute at the Madrigal with a stunning long-range shot, and his strike partner Llorente netted from a Robert Pires cross soon after.
Almeria's Argentine teenager Pablo Piatti pulled one back in the second half.
The visitors were the last team to beat Manuel Pellegrini's side in the league back in April but Villarreal were able to extend their unbeaten run to 16 between last season and the current campaign.
Valencia's Portugal midfielder Fernandes thumped a first-time shot inside the near post to break the deadlock in a scrappy game at the Coliseum.
Getafe lost striker Roberto Soldado to a foolish red card just before the break and it was one-way traffic from there on as Joaquin and Vicente both scored well-worked goals.
PENALTY MISSES
Sevilla are fifth with 20 points after Mali striker Frederic Kanoute returned from injury to score the only goal in a 1-0 home win over Andalucian rivals Recreativo Huelva.
Kanoute was left unmarked to head in a cross from the lively Jesus Navas in the second half, but went on to miss a later penalty.
Recre almost snatched an equaliser in a nerve-wracking finale but Sevilla survived to end a run of four straight defeats in all competitions.
Atletico Madrid were held to a 0-0 draw at bottom club Osasuna, and had France goalkeeper Gregory Coupet to thank for saving a first-half penalty.
They slip down to seventh with 14 points one short of Deportivo Coruna, who beat Espanyol 1-0.
It was Osasuna new coach Jose Antonio Camacho's first point since taking the helm four matches ago, but they remain without a win this season.
Fernando Llorente's last-minute header saved Athletic Bilbao and their coach Joaquin Caparros from a sixth consecutive defeat, grabbing a 3-3 draw away to Real Mallorca, having trailed 3-1 with 11 minutes to go.
