But Pep Guardiola's Barca side have added prolific Spain striker David Villa, combative Argentina midfielder Javier Mascherano and versatile Brazilian defender Adriano Correia.
Mourinho, a former assistant coach at the Nou Camp, got the better of Guardiola last season but it will be hard to mould the Real squad into an effective team in his first campaign.
If he does he will become the first man to lift the European Cup with three different clubs following his initial triumph with Porto in 2004.
Real are also in a tricky group, pitted against old rivals AC Milan, Ajax Amsterdam and Auxerre of France.
Barca, by contrast, are the finished article, boasting eight Spain internationals, including World Cup winners Villa, Xavi and Andres Iniesta, and should progress comfortably from a group with Rubin Kazan, Panathinaikos and FC Copenhagen.
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