Champions Real Madrid beat Mallorca 4-1 to break the 100-point barrier on the final day of La Liga season as Villarreal sensationally slipped through the relegation trapdoor.
Mesut Ozil scored twice while Cristiano Ronaldo and Karim Benzema also hit the target as Jose Mourinho's Real smashed Barcelona's previous record of 99 points from the 2009-10 season.
The Santiago Bernabeu was given the first chance to celebrate Mourinho's maiden Spanish title with 'los blancos' and resonated with a celebratory atmosphere to see skipper Iker Casillas lift the trophy after the match.
In the celebrations that followed, Argentine striker Gonzalo Higuain indicated he may be about to leave Madrid, with recent speculation linking him with a move to Paris Saint-Germain.
"They have been almost six great years here in which I have had to fight for everything. I'm very grateful to the club and I've always tried to show this whenever I've taken to the pitch, I hope everything turns out well," he said.
Mallorca needed a win to qualify for next season's Europa League and battled hard against a Real side who claimed their 32nd Spanish title two games ago.
Ronaldo headed home an 18th-minute opener and two minutes later Benzema finished off a swift passing move after receiving a Ronaldo pass to double the lead.
Ozil produced a delightful chip for the third on 50 minutes before Chori Castro pulled one back for the side from the Balearics.
German international Ozil added his second when he guided home a long cross from Marcelo eight minutes later.
Jose Rondon scored the goal that beat Sporting Gijon 1-0 and guaranteed Malaga their first ever qualification for the Champions League.
Defeat for Sporting means they drop into the second division after four successive seasons in the top flight.
The Andalusian side started the stronger and Juan Pablo in the visitors' goal had to make an acrobatic save from Eliseu on 17 minutes.
Then Rondon hit the post with a powerful header and with the game goalless at the interval Malaga's dream was on hold.
However, it was Rondon who headed home a corner on 49 minutes to ease the nerves and send the packed Rosaleda crowd into celebration.
Algerian striker Abdelkader Ghezzal scored twice to help Levante to a 3-0 win over Athletic Bilbao and reward their magnificant season with a Europa League place.
He raced onto a long ball from centre-half Gustavo Cabral to lob over the advancing Bilbao goalkeeper Gorka Iraizoz on the stroke of half-time for his first.
Jose Barkero supplied him for the second and Francisco Farinos got a last minute penalty to send Levante into European competition for the first time.
At the bottom, Villarreal were relegated along with Sporting in a dramatic 90 minutes in which any two of five teams were facing the drop.
Villarreal lost 1-0 at home to Atletico Madrid for whom Radamel Falcao scored with two minutes remaining to condemn last season's Europa League semi-finalists to the second-tier for the first time since 1998-99.
Coach Miguel-Angel Lotina, who suffered a similar fate last season with Deportivo La Coruna, was distraught.
"It's difficult to explain what has happened. After winning in Gijon we had it in our hands, but last week we conceded a late goal and tonight again with a header from a corner. Football has been very unfair with Villarreal," he said.
Marco Ruben and Marcos Senna went close from distance in a first-half in which the team battling relegation were the stronger.
All seemed under control until Falcao headed home and almost immediately a goal from Raul Tamudo for Rayo Vallecano at home to Granada turned things around completely.
Until that stage, Rayo Vallecano were in the relegation zone and 60 seconds from the drop.
Veteran striker Tamudo came off the bench to prod home a header from close range to send Villarreal to the second division and save the tiny club from the south of Madrid.
Antonio Galdeano 'Apono' and Hector Postiga gave Zaragoza the 2-0 win they needed at eight-man Getafe and finish a miraculous end of season in which they won eight out of the last 11 games to guarantee safety.
The home side had Pablo Sarabia sent-off for two yellow cards within seconds for protesting on 25 minutes.
Zaragoza also had cause to complain when the referee denied them a penalty when it seemed Postiga had been wrestled to the ground just before the interval.
On 56 minutes, Miguel Torres was also sent-off for a handball in the area and Apono hit home from the spot.
Zaragoza lost a man late on when substitute Tomislav Dujmovic was dismissed before Miku left the home side with eight players and Postiga scored a last minute second to seal their survival.