Barcelona trounced visitors Atletico Madrid 6-1 at the Nou Camp on Saturday to move into second place behind Villarreal in the Primera Liga.
Villarreal have 16 points from six games after coming from behind to beat Real Betis 2-1 while Barca are on 13 after a scoring spree led by a double from Samuel Eto'o.
Atletico, who enjoyed a good start to the season and have been on top form in the Champions League, are seventh with nine points after being taught a lesson by Pep Guardiola's side.
Atletico conceded three goals in the first nine minutes and were given little chance to make any impression on Barca's lead after Maxi Rodriguez pulled a goal back in the 13th minute.
Barca's first came after three minutes when Mexican defender Rafael Marquez headed home a well-placed corner from Xavi.
Three minutes later they got a penalty, after a scuffle between Czech defender Tomas Ujfalusi and Barca's Argentina forward Lionel Messi, which Cameroon striker Eto'o put away.
Messi's quick free kick in the ninth minute made it 3-0 as he caught the defence napping while they lined up the wall. The ball sailed into the top corner past Atletico's stunned France goalkeeper Gregory Coupet who barely moved from his post.
Atletico's Argentina midfielder Maxi Rodriguez took Barca's keeper Victor Valdes by surprise four minutes later to give the visitors their only goal of the evening.
But Barca quickly took control again as Eto'o skipped past the mesmerised Atletico defence and knocked the ball under Coupet to score his second and Iceland striker Eidur Gudjohnsen made it 5-1 just before the half-hour mark.
Barca's lead was extended in the second half after their France striker Thierry Henry replaced Eto'o and slammed home their sixth goal of the night after 73 minutes.
Earlier, Villarreal recovered from a shaky start against Real Betis, who are still waiting for their first league win.
The visitors dominated the first half and forced Villarreal on to the back foot as they took every opportunity to slip past the home side's defence.
A long pass from Betis's Chilean forward Mark Gonzalez in the 20th minute was scooped up by team mate Damia Abella who tapped the ball into the net to give them the lead.
Villarreal came out fighting after the break, though, and had several shots before Gonzalo Rodriguez headed home a free kick by Argentine Ariel Ibagaza to equalise in the 67th.
Betis then failed to clear after a goalmouth scramble and Villarreal striker Joseba Llorente struck the winner.