Diego Forlan scored a penalty to give Atletico Madrid a 1-0 Primera Liga win over visiting Valencia on Sunday and improve their chances of a lucrative place in next season's Champions League.
Barcelona clinched their first league title in three years on Saturday and Real Madrid are assured of second place with two matches left.
Third-placed Sevilla (64 points) and Atletico, who climbed to fourth (61), have the best chance of grabbing the remaining two spots in Europe's top club competition and Valencia and Villarreal are still in the hunt in fifth and sixth on 59.
Atletico took the lead from the penalty spot in the 29th minute at the Calderon.
Sergio Aguero burst through the centre and took the ball round Valencia goalkeeper Luis Cesar Sanchez before tumbling to the ground and the referee pointed to the spot.
Television replays showed the decision was harsh on Cesar but Forlan drove the ball low into the righthand corner to score his 28th league goal of the season, one short of Barca striker and Primera Liga top scorer Samuel Eto'o.
Valencia rarely threatened the home side's goal and Simao Sabrosa, Aguero and Forlan had chances to stretch the lead before Atletico wrapped up a fourth straight win.
Real Mallorca earlier came from behind to beat a weakened Barca 2-1 and spoil the new champions' celebrations.
Eto'o grabbed an early lead with his 29th goal of the campaign, but quick strikes from Juan Arango and Cleber Santana sealed the fightback for mid-table Mallorca in the second half.
Eto'o had a chance to level from the spot in the final minute, but struck his penalty against the base of the post.
Pep Guardiola sent out a number of youth players at the Ono Estadi with his focus turning to the Champions League final against Manchester United in Rome on May 27, and a possible third trophy to add to the King's Cup and the league title.
"My idea is that many players won't play until the final in Rome," Guardiola said at a news conference. "I don't want to risk anything."
In other matches, a diving header into his own net from Malaga's Helder Rosario earned Sporting Gijon a 2-1 home win that hauled them out of the relegation places.
Sporting climbed to 17th on 37 points, above Osasuna, who drew 0-0 with Sevilla on Saturday, on the head-to-head rule.
A controversial Jose Barkero late penalty gave Numancia a 1-0 win over rivals for the drop Recreativo Huelva. Recre are bottom on 33 points and Numancia have 35, two short of safety.
Victories for Real Betis, Racing Santander and Espanyol helped move them further away from the bottom three.