Barcelona preserved their 100 per cent start to the season with a stunning comeback at Sevilla, while Malaga are also still unbeaten in second spot.
Real Sociedad secured the bragging rights in the Basque derby and Valencia will hope beating Real Zaragoza has kick-started their season.
Leaders Barcelona made it six wins out of six after coming from 2-0 down to prevail 3-2 at 10-man Sevilla thanks to David Villa's stoppage-time winner.
Sevilla appeared on course to upset Tito Vilanova's side after Piotr Trochowski's 26th minute goal was followed up by Alvaro Negredo's effort three minutes after half-time.
Cesc Fabregas pulled a goal back on 53 minutes and Barcelona were given further encouragement when Sevilla's Gary Medel was sent off on 72 minutes.
Former Arsenal midfielder Fabregas levelled matters a minute from time before substitute Villa finished off a neat move in the third minute of injury-time to hand Barcelona the points.
Malaga maintained their unbeaten start to the season after a comprehensive 4-0 home win over 10-man Real Betis.
Visiting keeper Casto was sent off in the 10th minute for conceding a penalty and Malaga took full advantage, with Joaquin converting the resultant spot-kick.
Ignacio Camacho struck the post for Malaga midway through the first half before the lead was doubled on 28 minutes by Javier Saviola.
Antonio Amaya's own goal on 72 minutes compounded Betis' misery and the highly-rated Isco completed the rout with a fourth goal two minutes later.
Valencia picked up just a second league win of the season as Sofiane Feghouli scored and was later sent off in the 2-0 home success over Real Zaragoza.
Feghouli opened the scoring for Valencia on 12 minutes before Zaragoza came close to an equaliser early in the second half when Victor Rodriguez hit the crossbar.
The hosts responded with Jonas striking the post before Jonathan Viera did score a second on 59 minutes and, two minutes later, Feghouli was sent off for a second bookable offence.
Athletic Bilbao continue to struggle at the lower end of the standings after going down 2-0 away to Real Sociedad in the Basque derby.
Antoine Griezmann supplied Sociedad with a 62nd minute lead and former Arsenal forward Carlos Vela made certain of the points with a 71st minute penalty after Bilbao's Fernando Amorebieta had been sent off.