Los Blancos cruised to a 4-0 win thanks to goals from Gonzalo Higuain, Angel di Maria, Michael Essien and Luka Modric.
Mourinho is only the fifth man to reach the milestone, and it was all the sweeter as rivals Atletico Madrid lost their unbeaten run to Valencia.
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Liverpool have unveiled their new home kit for next season, sticking with the hugely popular retro styling of the current shirt.
The reputation of the Premier League means it is the most popular and one of the most watched leagues in the world.