Villarreal qualified for the Champions League after they ran out 2-0 victors against Valencia at the Mestalla on Sunday night.
First-half goals from Samu (14′) and Adrian (33′) saw the Yellow Submarine halt a three-match winless run as they pulled six points clear of Athletic Bilbao in fifth place.
Earlier in the day, Athletic Bilbao overtook opponents Celta Vigo in the La Liga standings with a 2-1 win at San Mames.
Los Leones had to come from behind to claim all three points, after Fabian Orellana gave the visitors a 14th-minute lead.
Aritz Aduriz (38′) restored parity from the penalty spot before the break and Raul Garcia (72′) completed the comeback win to lift the Basque outfit to fifth, one point ahead of Celta in sixth.
Meanwhile, Getafe gave their survival prospects a shot in the arm as they beat 10-man Deportivo La Coruna 2-0 at the Riazor.
Pedro Leon opened the scoring four minutes before half-time and Carlos Vigaray sealed the victory five minutes from time, with Celso Borges receiving his marching orders for the hosts on 64 minutes after picking up two yellow cards.
The Azulones moved up to 18th spot, level on 35 points with 17th-placed Sporting Gijon, while Depor extended their winless run to six outings to sit 15th in the table.
Elsewhere, Felipe Caicedo scored the only goal of the game as Espanyol clinched a narrow 1-0 win over Sevilla at the RCDE Stadium.
Caicedo struck seven minutes into the second half, which arrested a five-match winless streak for Periquitos, who pulled five points clear of the relegation zone in 14th place, as Los Rojiblancos suffered a fifth defeat in seven games.
Athletic Bilbao 2-1 Celta Vigo
Espanyol 1-0 Sevilla
Deportivo La Coruna 0-2 Getafe
Valencia 0-2 Villarreal