Cristiano Ronaldo header in injury time saw the Real Madrid aboard big rivals Barcelona in the second "El Classico" in four days of winning the Copa del Rey and to seal their first trophy under Jose Mourinho.
The first 90 minutes ended goalless, with Madrid at the top during the opening and Barca better after the break.
But despite the higher Catalan celebration in overtime, Mourinho's men looked dangerous on the break and Ronaldo after corner of a low shot narrowly wide, beating Portugal's Jose Manuel Pinto with a brilliant header from Angel di Maria graph .
Pinto started in goal in place of Victor Valdes as he had done throughout the competition.
Meanwhile, Barca captain Carles Puyol has been ruled unfit to start after his injury at 1-1 on Saturday night in Madrid, take the First Division, with Javier Mascherano slots alongside Gerard Pique in central defense.
Mesut Özil Mourinho returned after the German player began on Saturday are based on the bench.
In this, the second series of meetings Classic four, with a two-legged semi-final to get into the Champions League next week, the Portuguese have kept faith with Pepe in the midfield shield with three men Sami Khedira and Xabi Alonso.
And it worked from the beginning as Madrid, Barcelona postponed, which appears to the surprise of the Catalans to be put into the game dynamically
Ronaldo, playing against Mourinho has opted for a permit three forwards - Gonzalo Higuain, Karim Benzema and Emmanuel Adebayor - on the bench, was about to give his side the lead after 12 minutes when he beat a very close Pinto , but saw the ball on line hack Mascherano.
Madrid defender Alvaro Arbeloa was lucky to escape with a light shade on David Villa at the end of the half things went wrong.
The defender escaped without caution, but both Pepe and Pedro have found their way into the referee's book before the break, both teams continued to compete near the edge.
But in terms of football, Madrid had the advantage.
Pinto saved well from Ronaldo 10 minutes before the break but substitute goalkeeper is misplaced just before the break and had the opportunity to see Pepe rebound in the post header.
However, Barca began the second half of the front foot moves up a gear after a disappointing opening 45 minutes.
Pedro shot narrowly wide, Lionel Messi to jump over the bar and the Argentine striker was created almost Dani Alves, the Catalans have found their rhythm.
And they thought they had taken the lead after 68 minutes when Villa, who had not scored for 10 games, closed with a ball from Messi after the Argentinian had brilliantly beat three players from Real Madrid, and dividing the shot bass beat Iker Casillas, but the flag was an assistant and the Spain striker's effort was correctly excluded.
However, Barca were dominant and that now seemed a good sign for Madrid.
Casillas made two good saves in a minute to deny Messi and Pedro, while Argentina has stopped short, seemed to waltz through the defense of Madrid.
But Madrid weathered the storm and the result remained goalless after 90 minutes.
The first overtime period was dominated by Barca, but the best chance fell to Ronaldo, who raced clear on the right flank and the load in the region, driving a skimming shot just wide of the goal.
But the Catalans have ignored the warning and five minutes later they were back.
Marcelo played a one-two with Di Maria, who sent a deep cross and inviting the search box from Ronaldo, who rose majestically to power home a header at the far post.
Ronaldo would have wrapped up two minutes before the finals, but selfishly kept the ball in the area and his shot was blocked over time.
But Real were willing to seal a famous victory and the end of a period of almost three years without a trophy. The only sour note for Mourinho's men was the last dismissal Di Maria after winning a second yellow card for a foul on Messi.