David Villa fired Valencia to a 2-0 victory over Athletic Bilbao at the Mestalla to guarantee Europa League football for the cash-strapped club.
In what could be his final game for Los Che, Villa opened the scoring on seven minutes when he fired home from inside the area.
Both sides had plenty of chances to score in the aftermath, but Valencia looked much the stronger and Villa could easily have doubled their advantage when he went clean through shortly before half time.
Substitute Inigo Velez came close to levelling as he raced clear 10 minutes after the break, and Bilbao had an effort cleared off the line shortly afterwards, but Valencia were soon back on top and Villa had two further chances to double his tally while Vicente also had a low drive turned away.
Bilbao defender Mikel Balenziaga received a second yellow card on 77 minutes for an over-the-ball challenge on Herrero Michel and, after passing up a golden chance on 85 minutes, Villa finally bagged his second when he turned the ball home at the far post in the final minute.
The result ensures Valencia finish sixth, while Bilbao would drop to 14th if Real Valladolid beat Real Betis on Sunday.
Atletico Madrid, meanwhile, are certain of a Champions League place after their 3-0 win over mid-table Almeria.
Sergio Aguero gave them the lead on 19 minutes before Raul Garcia headed home from close range on 27 minutes and, shortly after the break, Diego Forlan fired in the third from distance.
The result leaves them level on points with fourth-placed Sevilla, who need just one point against relegated Numancia on Sunday to clinch third.
Atletico boss Abel Resino said: "We have achieved our target.
"When I arrived in February, we were a long way away from our dream and had plenty of work to do, but we succeeded.
"I arrived when the team was in trouble and I had a massive task. It was a team without unity but now they are all together.
"That is the basis for success.
"On Monday, we will sit down to discuss whether I will continue in the role."
Champions Barcelona rescued a last-minute point at Deportivo La Coruna despite fielding an under-strength side.
Samuel Eto’o, Xavi, Yaya Toure and Gerard Pique were the only first-choice players selected for the match, and they looked set to sign off their treble-winning season with a defeat when Rodolfo Bodipo headed home after 31 minutes.
However, in the last minute, Eto’o fired into the top corner from Bojan Krkic's through-ball to snatch a point.
Villarreal ensured they took fifth with a 3-2 win at ninth-placed Real Mallorca.
Cani put Villarreal ahead on 28 minutes and, although Aritz Aduriz drew them level on 36 minutes, Joseba Llorente scored goals either side of half time to make it 3-1.
Pierre Webo pulled a goal back for Mallorca in the 90th minute but it was to no avail.