Karim Benzema gave the hosts an early lead but Lionel Messi levelled to become the the Clasico's joint all-time top scorer.
Sergio Ramos headed in a corner to restore Madrid's lead with nine minutes remaining as Mourinho's men wrapped up a late victory.
And the game ended in controversy as Barca keeper Victor Valdes given his marching orders on the final whistle for a second yellow card after arguing with referee Miguel Angel Perez Lasa.
Mourinho, presumably with an eye on the second leg of Real's last-16 Champions League tie with Manchester United, put out a vastly different team to the one that beat Barcelona last Tuesday in the semi-final of the Copa del Rey.
Cristiano Ronaldo, Mesut Ozil, Sami Khedira, Gonzalo Higuain and Alvaro Arbeloa all started on the bench, with Kaka, Benzema, Luka Modric, Alvaro Morata and Michael Essien drafted in.
Barcelona fielded an almost identical line-up with the exception of Cesc Fabregas and the injured Xavi, who made way for Thiago Alcantara and David Villa.
Morata picked the ball up on the left wing, beat Dani Alves and delivered a low cross across the box which Benzema tapped in from close range.
Alves delivered a low through-ball into the path of Messi after the Madrid defence and keeper Diego Lopez hesitated. Unchallenged, the Argentinian drove into the box and shot into the bottom corner to equalise.
It was Messi's 39th league goal of the season and his 18th in a Clasico, drawing him level with fellow Argentine Alfredo Di Stefano.
The opening stages of the second period were largely uneventful but the double substitution of Ronaldo and Khedira for Kaka and Benzema lifted the Bernabeu faithful.
Ronaldo forced a save from Valdes with a stinging free-kick and then a few minutes later shot into the side-netting.
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