Lionel Messi scored a hat-trick as Barcelona beat Deportivo La Coruna in an incredible nine-goal thriller, while Real Madrid beat Celta Vigo and there were also wins for Malaga and Valencia.
Deportivo have endured a tough start to the season and the last thing they needed in their quest to climb the standings was to run into a Barcelona side in full flow, who prevailed 5-4 to consolidate top spot.
It was a devastating display of attacking football from Barca, which started in the third minute when Jordi Alba fired home after being played in by Cesc Fabregas' though-ball.
Cristian Tello showed good skill before lashing in a second for Tito Vilanova's side, and Lionel Messi then made it 3-0 with a fine strike from outside the area following Fabregas' back-heel.
Deportivo fought hard to get back into the game as Pizzi netted from the penalty spot and Victor Valdes allowed Alex Bergantinos' effort to slip through his fingers.
Messi latched on to another delightful Fabregas pass to put Barca 4-2 in front at the end of an incredible first half, but the drama was not over there as Pizzi curled in a stunning free-kick to give Depor hope once again at the start of the second period and Javier Mascherano was sent off for a second bookable offence.
Messi completed yet another hat-trick following a superb run and finish, but Depor were still not done and a late Alba own goal ensured a tight finish.
Gonzalo Higuain's cross-cum-shot and a penalty from Cristiano Ronaldo helped injury-hit Real Madrid to a comfortable, if uninspiring, 2-0 victory over Celta Vigo.
The recent international break has left Madrid short of options at the back, with full-backs Marcelo, Fabio Coentrao and Alvaro Arbeloa facing spells on the sidelines, but they attacked from the off and took the lead in the 11th minute thanks to Higuain's slightly fortunate goal.
Ronaldo netted from the spot midway through the second half to settle matters after Mesut Ozil tumbled in the area following a rather innocuous challenge from defender Gustavo Cabral.
Malaga leave it late
Joaquin scored the winner three minutes from time as Malaga came from behind to beat 10-man Valladolid 2-1.
Manucho had fired the visitors into a shock lead on just nine minutes but Isco levelled the scores eight minutes before half-time with an accurate low finish from Eliseu's cut-back.
The game appeared to being going Malaga's way when Manucho was harshly sent off for a second yellow card nine minutes from time and then the hosts were awarded a penalty when Henrique Sereno felled Javier Saviola in the area, but Joaquin blazed his spot-kick over.
However, the former Spain international made amends two minutes later when he pounced after Dani Gimenez could only parry Martin Demichelis' header back into the danger area.
Valencia snatched a 3-2 victory away from 10-man Athletic Bilbao with two late goals in a match between two of the Primera Division's most notable early-season strugglers.
Aritz Aduriz's first-half double, either side of a Roberto Soldado penalty, looked like it would be enough for Bilbao despite Ander Herrera's dismissal on 67 minutes.
But after Tino Costa levelled with just two minutes remaining, substitute Nelson Valdez popped up to head in the winner with barely any time left on the clock.