The Portuguese was in mischievous mood as his team progressed to the Champions League semifinal stage, suggesting that the Catalan side is guaranteed a showpiece spot
The Madrid boss, speaking after his side's 5-2 win over APOEL at the Santiago Bernabeu on Wednesday, claimed a meeting with his former side Chelsea at Munich in May is impossible.
When asked about the two semifinals in a television interview in the tunnel straight after the final whistle, Mourinho told TeleMadrid: "For me the big question is knowing who will play against Barca in the final.
"It will be a great semifinal, Bayern against Real Madrid, and the best team will go on to play against Barca."
Mourinho then walked away from his interviewer, who quickly followed up by asking the Portuguese why he was so certain that Barcelona would be in the final.
"Because they are very good." the Blancos boss added, before abruptly ending the interview.
Barca will first face Chelsea in the last four of the competition later this month, in a semifinal tie identical to the one the Catalans won in Pep Guardiola's first season, 2008-09, en route to the trophy, and which was marked by refereeing controversies in the second match in London.
Mourinho later said he would be 'ashamed' to win in such circumstances, describing the game as 'the scandal of Stamford Bridge'.