Mourinho saw his own side ease into the final four with an 8-2 aggregate victory over APOEL Nicosia, and they will now face final hosts Bayern Munich in the next round. But should Mourinho's side go through, the Portuguese does not expect to find his old team waiting in Munich.
Asked why he had told Telemadrid that Barcelona would advance, he said: "Because they are very good. Barcelona aren't the favourites, they are super-favourites."
He added: "Let me be honest, I don't think the final will be a Real Madrid/Chelsea final. It could be Bayern or Barcelona, I just don't think it will be Real Madrid v Chelsea and we know why."
The Spanish league leaders completed an 8-2 aggregate thrashing of APOEL that is unlikely to have taught Bayern very much that they did not already know about their next opponents.
Mourinho's men maintained their 100 per cent home record in the tournament this year with a 5-2 second leg win at the Bernabeu against the valiant but limited tournament surprise package.
Leading scorer Cristiano Ronaldo bagged a brace, including a swerving and dipping free kick, to take his season tally to 49.
Kaka curled in a sumptuous long-range effort, the busy Jose Callejon came off the bench to notch Madrid's fourth and Angel Di Maria continued to work his way back to full fitness after injury as he came on at the end to lob a fifth.
The La Liga leaders have scored 100 goals in their 30 league matches this season and in Europe have racked up 32 in 10 so far.
"The team are in good shape and we are well prepared for a difficult April," Mourinho said.
"Bayern is a very powerful opponent. It is a team I know well as it is almost the same side that I played when coach of Inter Milan in the Champions League final two years ago and they have great individual players.
"The players and myself are looking forward to what should be a great semi-final.
Having won 3-0 in Cyprus last week, and with a tough league clash at home to third-placed Valencia on Sunday, Mourinho was able to rotate some of his players though, as ever, Ronaldo started and finished.
"We wanted to build a team to win the game," Mourinho said. "Because I didn't think it was possible for APOEL to score four, we wanted to rest a few players and we attempted to balance things.
"We wanted to rest Marcelo and (Esteban) Granero so we substituted them and there might have been a few defensive errors towards the end, but I don't have any criticism, just positive words for a group that have reached this stage for two seasons in a row."
Conceding two goals at home to the unheralded Cypriots, a breakaway from Gustavo Manduca that made it 2-1 after 67 minutes and a penalty given away by Hamit Altintop near the end, was of no particular concern to Mourinho.
"I am not going to criticise anyone for the odd loss of concentration, because over the last two years this group of players have given their all," he said.
APOEL bow out with their heads held high after grabbing two surprise goals which were loudly hailed by their colourful and raucous group of travelling fans.
"The final result was fair. They were better than us but we leave satisfied," APOEL coach Ivan Jovanovic said.
"The important thing is the result was not terrible and we managed to score as well. There were lots of goals and the fans will have enjoyed it."
"It's been a great year for us. We were the only team left who started out on the 12th of July. It was our 16th match and we don't have a big squad. We worked hard to get here and we deserved it. The Bernabeu was a fitting place to end our run."
Mourinho gave them a glowing tribute. "Theirs is the biggest achievement in the Champions League this year. If Barcelona, Bayern or us go on to win, it won't be as big and achievement as theirs has been."