Real Sociedad stunned Malaga away from home, Real Zaragoza were involved in an eight-goal thriller and Osasuna gained a much-needed win in La Liga.
Malaga fluffed the chance to move back into the top three after suffering a 2-1 home defeat at the hands of Real Sociedad.
Carlos Vela put Sociedad in front inside the first minute and Xabi Prieto then scored a 59th minute winner after Javier Saviola had equalised for Malaga on 37 minutes.
Helder Postiga scored twice as Real Zaragoza roared back from two goals down to beat 10-man Deportivo la Coruna 5-3 in a crazy game at La Romareda.
The visitors had gone into an early 2-0 lead thanks to goals from Bruno Gama and Riki, but Apono brought Zaragoza back into the game from the penalty spot before half-time.
Pizzi was then shown a second yellow card for diving four minutes into the second period, and the hosts made their man advantage pay in spectacular style as Paco Montanes and Alvaro Gonzalez put them 3-2 in front before Postiga bulleted in two headers from excellent crosses by Victor Rodriguez.
Rodolfo Bodipo got one back for Depor in the last attack of the game but it mattered little, as Zaragoza moved into the top half of the table with their fourth victory in five games.
Primera Division bottom side Osasuna ended a run of five straight away defeats in emphatic style with a 3-0 win fellow strugglers Espanyol.
Osasuna had just one win from their opening 10 league matches and had lost all of their games on their travels, yet they never looked back after taking the lead through Alvaro Cejudo midway through the first half.
The 29-year-old former Las Palmas midfielder then teed up Kike Sola in the 63rd minute before Manuel Omwu added further gloss to the scoreline 12 minutes from time.
Rayo Vallecano produced a stunning second-half comeback to beat 10-man Celta Vigo 3-2 at Vallecas.
Iago Aspas had fired the visitors into a two-goal lead with two fine finishes in the first half, but the game swung in Rayo's favour five minutes before half-time when defender Gustavo Cabral was shown a second yellow card.
Leo Baptistao and Tito then headed the hosts back on level terms after the break and Piti sealed the comeback with a penalty eight minutes from time.