Villa was unlucky to be pulled up for offside and Casillas did well to come off his line to stop Pedro again as Madrid was in danger of being overrun.
Ronaldo showed his frustration in an incident with Barca coach Pep Guardiola, which earned him a yellow card, before Pepe was also booked for pulling Messi back.
The first half had been totally Barca's and Mourinho responded by replacing Ozil with Lassana Diarra at the start of the second half to play with three central midfielders.
It had little effect as Messi set up Xavi, who should have scored rather than hit the side netting with Casillas being beaten just a couple of minutes before Villa scored Barca's third after another piece of Messi's magic.
The same pair combined for Villa to score the fourth after 57 minutes as Barcelona threatened to run rampant and the only real surprise was that the final goal didn't arrive until injury time when the two substitutes Bojan and Jeffren combined for Jeffren to make it 5-0.
Moments later Sergio Ramos was sent off for a brutal foul on Messi to end a miserable night for Real Madrid.
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