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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The reputation of the Premier League means it is the most popular and one of the most watched leagues in the world.
Five English clubs will compete in the last sixteen of the Champions League for the first time ever as Liverpool, Manchester United, Manchester City, Chelsea and Tottenham face some difficult away matches.