Atletico Madrid overcame the heroics of Valencia goalkeeper Diego Alves to win 2-0 at the Mestalla.
The Brazilian saved two penalties, but second-half strikes from Antoine Griezmann and Kevin Gameiro settled matters.
The result keeps Diego Simeone’s side in early-season contention for La Liga glory. However Valencia, who replaced Pako Ayestaran with Cesare Prandelli as head coach this week, continue to struggle near the bottom.
The Basque side had reeled off four successive La Liga wins coming into this game and an assured finish from Aritz Aduriz in the third minute looked like it would set up another.
But the pivotal moment was the red card shown to Athletic full-back Mikel Balenziaga, who retaliated when Roberto Rosales left a boot in on him after a defensive tackle.
Balenziaga may face further sanctioning after remonstrating with the referee for several minutes before departing, and his team-mates were unable to hold on without him as quickfire goals inside the last 10 minutes from Sandro Ramirez and Duda earned the Andalusians just their second win in seven league matches.
The home side also finished with 10 men as defender Bakary Kone was sent off in the dying seconds.
Villarreal remain unbeaten in La Liga after securing a goalless draw away to Espanyol.
Villarreal were held to a goalless draw by Espanyol
The Yellow Submarine’s journeys this week had taken them from Bucharest, where they drew 1-1 with Steaua in the Europa League on Thursday night, to Barcelona and a point apiece with Quique Sanchez Flores’ men was probably the correct result on the balance of play.
Espanyol edged out of the relegation zone with the point, but still have just one win to their name after seven matches.
Elsewhere, Barcelona suffered a 4-3 defeat to Celta Vigo , while
Real Madrid were held to a 1-1 draw at home by Eibar.