Real Sociedad pulled clear of the La Liga relegation zone with a 2-0 win over Sevilla.
Valencia hit five to beat high-flying Celta Vigo, while Eibar continued their rise up La Liga with victory over Getafe.
Eibar maintained their top-six La Liga position after an own goal gave them a 1-0 victory over Rayo Vallecano.
Sevilla thrashed Getafe 5-0 in La Liga on Saturday night, while Granada drew with Real Betis and Malaga saw off Deportivo.
Sevilla came from behind to salvage a point at Eibar but their unconvincing away form continues.
Barcelona and Real Madrid will start their Copa del Rey campaigns against third-tier clubs.
A hat-trick from Brazilian striker Charles saw Malaga beat David Moyes' Real Sociedad 3-1 and get off the winning mark this season.
In his live Q&A, Sky Sports Guillem Balague said there is no interest from Barcelona in Liverpool's Philippe Coutinho.
Scroll down to see how Real Madrid were thwarted by Malaga in La Liga.
Real Madrid were held to a goalless draw by Malaga despite outplaying Javi Gracia's side at the Bernabeu.
Villarreal moved level with Real Madrid and Celta Vigo at the top of La Liga as they won 1-0 at Malaga in a late kick-off.
Raul Garcia enjoyed a dream debut as Athletic Bilbao eased to a morale-boosting first win in La Liga this season.
Thomas Vermaelen was the unlikely hero as Barcelona laboured to a 1-0 home win over Malaga in La Liga on Saturday.
Jon Driscoll is joined by Terry Gibson to discuss the weekend's action, while Guillem Balague speaks with Arsenal's Mikel Arteta.
All the action as it happened as Barcelona earn a narrow win over Malaga thanks to Thomas Vermaelen's second-half goal.
Once hailed as Spain's best player, we look at Joaquin's emotional return to Real Betis.
Sevilla had Steven N'Zonzi sent off as they were held to a goalless draw by Malaga in the first game of the La Liga season.
Sky Sports will remain the home of La Liga for another three seasons thanks to a new broadcast agreement announced today.
Derby defender Raul Albentosa is poised to join Malaga on loan.
Rafael Benitez's first El Clasico will be at the Bernabeu, with the return fixture taking place in Barcelona in April.