Madrid trail 2-1 from the first leg of the Champions League semi-final but Mourinho feels his players' composure bodes well as he looks to set up a possible showdown in the final against his former club Chelsea.
Mourinho's side beat Barcelona 2-1 at the weekend to move seven points clear at the top of the Primera Division with just four games remaining, and the Portuguese is closing in on both domestic and European silverware.
He said: "I don't know if the Champions League is more important than the league, because the best team always wins the league and this isn't always the case in Europe.
"However, the final of the Champions League is the most important thing in football.
"Today is almost like a long-awaited final, but I see calmness in the players. I don't like an excess of emotion, nor a lack of it."
Mourinho yesterday claimed he had been bereft of fortune in previous matches at the last-four stage after twice losing to Liverpool (in 2005 and 2007) - when at Chelsea - and again to arch-rivals Barcelona last season - a defeat he blamed on a UEFA conspiracy.
"Overall I have not been lucky in semi-finals of the Champions League," he said.
"I lost one with Chelsea (2005) due to a goal that wasn't a goal, the ball didn't cross the line. Another season (2007) we lost on penalties and when you lose a semi-final on penalties it is due to bad luck and I lost the semi-final last season because of what everyone knows."
Bayern Munich coach Jupp Heynckes is preparing for a "battle of the giants".
He said: "It is going to be spectacular. It is going to be a real treat with everything which belongs in such a football game.
"Just a fortnight ago, people were saying that Barcelona are the be all and end all, but now Real have gone and won in Barcelona.
"It will be a battle of the giants. Both clubs have a great history and I am looking forward to it, and I hope it has a positive outcome for us."
Heynckes expects Real to attack his side, but he is not going to set his side up to build a wall in front of the goal.
Instead, he has promised his team will play their part in the spectacle by remaining faithful to the style of play which has seen them score 71 goals in the Bundesliga and 27 times in Europe.
"We are capable of scoring at the Bernabeu," he said at a press conference in the Spanish capital. "At the same time, we have shown that we don't concede many.
"The first-leg result gives us a small advantage, but Real have amazing goalscoring potential and have scored nearly 150 goals so we will be prepared for that."
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