The host had failed to win in its last seven home meetings with Barca but went about ending that record early on with goals in the first 20 minutes from Gonzalo Higuain and Cristiano Ronaldo.
The visitor was then reduced to 10 men as Adriano was shown a straight red card for denying Ronaldo a clear goalscoring opportunity, but it regained its composure and was brought back into the game by a stunning free-kick from Lionel Messi just before half-time.
Chances continued to come at both ends after the break but Real failed to make its man advantage count and was nearly made to pay as Messi shot just inches wide deep into stoppage-time.
Real had failed to win any of its previous three games this season but it did not seem like a side lacking in confidence as it stormed out of the traps early on.
Higuain should have opened the scoring on seven minutes when his low effort across Victor Valdes was well blocked by the goalkeeper, but the Argentinian was gifted his goal only two minutes later by compatriot Javier Mascherano as the Barca defender misjudged a long ball forward from Pepe and allowed Higuain to run through and this time finish low beyond Valdes.And it was two just nine minutes later as Ronaldo pounced on an error this time by Gerard Pique. The Portuguese brilliantly back-flicked the ball into his path and, despite a poor second touch, his powerful shot rebounded in off Valdes' body.
The chances continued to come for Real as Valdes again denied Higuain from a narrow angle before Pepe had a header controversially ruled out for a push on Mascherano.
Part of Barca's disorganisation at the back could possibly be put down to a late change in the starting line-up as the injured Dani Alves had to be replaced by Jordi Alba with Adriano moving to right-back, and the Brazilian's torrid evening only lasted 27 minutes as he hauled down Ronaldo when he seemed set to break free on Valdes once more.
After another unsettling five-minute period for the Catalan side, new coach Tito Vilanova eventually introduced Martin Montoya for Alexis Sanchez and a return to four at the back seemed to offer the visitor some comfort as it began to make an impression on the game.
Montoya was inches away from converting a vicious low cross from Andres Iniesta before Messi did eventually halve the deficit moments before the interval with an incredible swerving free-kick from 30 yards.Ronaldo nearly responded with a long-range effort himself that flew just past and Angel Di Maria also shot narrowly wide as Madrid ended the half threatening a third.
However, at the start of the second period, it was Barca's tiki-taka that began to dictate play as the pace of the game dropped markedly.
Pedro very nearly scored a carbon copy of his goal in the first leg as Mascherano's perfectly-weighted pass saw him through on goal but his prodded finish did not have enough power to get through Iker Casillas' legs and the Spain captain collected at the second attempt.
Sami Khedira then nearly restored Real's two-goal cushion but was denied by another fine Valdes save at the end of a brilliant run.
Barca remained dangerous, though, and another brilliant piece of play from Messi released Alba through on goal, but he just over-ran the ball as he rounded Casillas and was eventually crowded out.
Higuain should have given Real breathing space with 11 minutes remaining but he hit the outside of the post with only Valdes to beat and that miss nearly cost his side as Barca came desperately close to equalising in stoppage-time.
Firstly, Montoya was denied by a solid save from Casillas before Messi seemed destined to hand Barca the cup as he found space on his favoured left side just outside the area but the ball slipped just wide and Real clung on for its first Supercopa title in four years.
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