Ronaldo put Real in front with a header following Mesut Ozil's corner before Diego Costa levelled.
He produced a composed finish after Radamel Falcao's pass before Real hit the post three times through Ozil, Karim Benzema and Ronaldo.
But Joao Miranda's extra-time header secured a famous victory for Atletico.
In a bad-tempered Madrid final, Atletico also finished with 10 men as Gabi was ordered off after encroaching at a free-kick to earn a second yellow card.
But the visitors held on to cap a disastrous night for Real and their manager Mourinho, who has hinted that he could leave when the season ends in two games time.
Defeat means the former Chelsea boss, who has been linked with a return to Stamford Bridge, ends the campaign without any major silverware.
Mourinho was sent from the bench for protesting a referee's decision in the 76th minute.
The Portuguese reacted furiously when the official awarded a free-kick to Atletico, racing to the edge of his technical area and gesticulating wildly.

Ronaldo followed his manager down the tunnel six minutes from the end of extra-time, the former Manchester United player appearing to flick out his boot at Gabi's face after a challenge on him by the Atletico player.
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