David Trezeguet struck twice as Hercules claimed their second big scalp on their return to the top flight with a 2-0 win over Sevilla.
The former France forward, a summer signing from Juventus, bagged his first goals for the club before the break to seal an impressive victory for the Alicante side, who beat Barcelona at the Nou Camp earlier this month.
Atletico Madrid emerged with a narrow 1-0 victory against bottom side Real Zaragoza in a lively encounter at Vicente Calderon Stadium.
Diego Costa netted the only goal after 20 minutes before Jose Antonio Reyes was sent off just after the hour for running into the back of Matteo Contini, who appeared to stop in front of the Atletico striker in an effort to encourage the collision.
The win lifts Atletico into fourth place while Zaragoza continue to prop up the rest with just two points from their opening five games.
Espanyol climbed into the top six of La Liga this courtesy of a 1-0 victory over 10-man Osasuna at Cornella.
Young debutant Alvaro Vazquez scored the only goal of the game for the Barcelona side, who were playing with an extra man from the 21st minute following the sending-off of Lolo.
Fernando Cavenaghi scored twice as Real Mallorca condemned newly-promoted Real Sociedad to their third consecutive league defeat.
Cavenaghi opened the scoring after seven minutes before he made the game safe with his second in the 62nd minute. Mallorca's 2-0 win ensured they stayed unbeaten at home this season.
Getafe defeated Racing Santander 1-0 to put their season back on track following Thursday's disappointing home defeat to Malaga.
Victor Sanchez struck the only goal of the game after 16 minutes and that was enough to see off a Racing side who finished with 10 men following the dismissal of striker Markus Rosenberg.
Kalu Uche's early brace earned Almeria a 2-0 win against 10-man Deportivo La Coruna. Uche opened the scoring in the fifth minute at the Riazor before adding his second in the 19th minute to help second-bottom Almeria take control against winless Depor.
The night got worse for the Galician side when they lost centre-back Diego Colotto to a straight red card in the 42nd minute.