Real Madrid made it two wins from two against Getafe, while Barcelona were held at Real Sociedad.
Jose Mourinho's Real Madrid maintained their perfect start to the season with a 4-2 win over Getafe at the Bernabeu.
Karim Benzema fired the home side in front after just 14 minutes, but Miku drew Getafe level six minutes before the break.
Cristiano Ronaldo restored Real's lead on the hour with a controversial penalty and Benzema added a third nine minutes later.
Getafe refused to give in with Miku reducing the arrears with his second of the contest on 73 minutes, but Gonzalo Higuain came off the bench to seal the win with Real's fourth two minutes from time
Barcelona threw away a two-goal lead as Real Sociedad snatched a superb and deserved 2-2 draw at the Estadio de Anoeta.
Two goals in as many minutes from Xavi and Cesc Fabregas put Barca 2-0 up inside the opening quarter-hour to put them in firm control.
However, Sociedad hit back with two goals in two minutes in the second half to stun Barcelona.
Imanol Agirretxe headed home Xabi Prieto's cross on 59 minutes and Antoine Griezmann's bizarre goal two minutes later drew the home side level.
David Villa's dreadful pass from inside the Sociedad half sent Agirretxe through on goal and the forward's lob was pushed on to the bar by the hand of Sergio Busquets, but Griezmann followed up to head into the empty net.
After some confusion over whether the goal had been awarded the referee gave the goal to Sociedad.
Barcelona tried to rally in a bid to find a winner, but Sociedad held on for a share of the spoils.
Valencia maintained their 100 per cent start to the season with a 1-0 win over Atletico Madrid at La Mestalla.
Roberto Soldado scored the only goal of the game on 52 minutes when he headed home Miguel's cross.
Ten-man Villarreal picked up their first point of the season after a 2-2 draw with Sevilla at El Madrigal.
Villarreal were reduced to ten men when goalkeeper Diego Lopez was sent off for a foul on Diego Perotti on 22 minutes.
Alvaro Negredo's resulting penalty was saved by Cesar Sanchez but the striker fired home the rebound.
Villarreal drew level from a penalty of their own 12 minutes later with Giuseppe Rossi scoring from the spot.
Marco Ruben gave ten-man Villarreal the lead on 72 minutes, but Sevilla secured a draw three minutes from time when Alexis headed home.