Iago Aspas struck twice as unbeaten Celta Vigo shattered Barcelona's 100 percent start in La Liga with a 4-1 win at Balaidos.
Ex-Barca youngster Nolito also continued his fine start to the season with a stunning opener and substitute John Guidetti struck for rampant Celta after Neymar had claimed a consolation.
Celta's victory lifted them above Barca in the Primera Division and was reward for an enthusiastic display.
Karim Benzema scored twice as Real Madrid held on for a 2-1 win at Athletic Bilbao.
The visitors were gifted an opening goal as Benzema pounced on a schoolboy backpass from Mikel San Jose in the 19th minute.
Sabin Merino equalised for Athetlic in the 68th minute, but the hosts' joy lasted less than two minutes before Benzema scored his second.
Cristiano Ronaldo was made to wait to score his 500th goal for club and country as he was held without a tally for the second straight game.
Villarreal moved level with Real and Celta as they won 1-0 at Malaga in a late kick-off.
Fernando Tissone's 71st-minute own-goal was enough to secure all three points for the Yellow Submarine, who won their fourth league game in a row.
Levante came back from 2-0 down to salvage a point at home to Eibar.
Borja thought he had handed Eibar their third win of the Primera Division campaign with a well-taken brace, but Levante hit back through Jose Luis Morales and Acosta Deyverson at the death to draw 2-2.
The point is enough to lift Levante out of the drop zone and up to 14th, while Eibar drop to seventh.
Rayo Vallecano picked up their second win of the campaign as a 2-1 success at home to 10-man Sporting Gijon also made it back-to-back victories for coach Paco Jemez.
Vallecano made the most of their man advantage after Gijon skipper Bernardo was shown two quick-fire yellow cards in the first half, and they were 2-0 up thanks to Roberto Trashorras and Javi Guerra.
Jony halved the deficit for Gijon but despite their efforts, the home side held on.
In the day's remaining game, Sevilla continued their poor start to the season as they lost 2-0 to Las Palmas.
Roque Mesa opened the scoring for the side from the Canaries on the half-hour and Antolin Alcaraz sealed the win with 14 minutes remaining.
The result leaves Sevilla winless and bottom of the league while Las Palmas leapt into mid-table with a first triumph of the campaign.