Real Madrid lost top spot in the Primera Division after being held to a surprise goalless draw by promoted Levante at the Ciudad de Valencia.
It was a frustrating evening for Jose Mourinho's side, who made virtually all the running but could find no way through a Levante defence that had conceded 10 goals in their opening four games - the worst record in La Liga.
Madrid came into the match having picked up 10 points from their opening four games but without hitting top gear and without making the most of the chances they have been creating.
And it was a similar story as the big-spending Spanish giants dominated for large spells but with nobody being able to beat Levante goalkeeper Manuel Reina, who helped his side claim their first points at home to Madrid after five previous defeats against the capital club.
Barcelona were made to work hard in the pouring rain at San Mames but secured a convincing 3-1 victory over Athletic Bilbao to move up to second place in the Primera Division.
The Catalans did not have things all their own way in an even first half but their task was made simpler after Fernando Amorebieta was dismissed for an ugly challenge on Andres Iniesta in the opening period.
Seydou Keita and Xavi both struck after the break to put Catalans in control, and even though Igor Gabilondo gave Athletic hope late on following David Villa's sending-off, Sergio Busquets clinched victory for the visitors in added time.
Valencia struck twice in the first 10 minutes to beat Sporting Gijon 2-0 and continue their excellent start to the season.
The goals from Mehmet Topal and Roberto Soldado secured a fourth win in five Primera Division matches for Unai Emery's side.