Mourinho's predecessors, Carlo Ancelotti, Xabi Alonso and Alvaro Arbeloa, struggled to strike a balance between attack and defence while lining up with Kylian Mbappe, Vinicius Junior and Jude Bellingham.
Madrid won the Champions League in 2024 with England international Bellingham and Brazilian winger Vinicius playing key roles, but since French superstar Mbappe arrived that summer, the club have not lifted a major trophy.
"They are incredible players and incredible players want to play with incredible players," Mourinho told reporters.
"Tactically, it could be tricky. Ancelotti has found a set-up with Brazil perfect for Vini, (Didier) Deschamps has found one with France perfect for Kylian, (Thomas) Tuchel one perfect for Jude; it's harder for Mourinho to do it for the three of them.
"We're on it. I want the three, when all three play, to feel comfortable on the pitch... they are three players of great quality.
"They don't play in incompatible positions. We will have a great season with them."
However, Madrid's stars can consider themselves warned - they must contribute in defence this season.
"We have to defend with 11 players," said Mourinho.
"If a team is pushing us back and giving us problems in our final third, we all have to defend."
Mourinho said in his second spell at Real Madrid, after previously coaching the team between 2010-2013, he hopes his players make life hard for him in terms of team selection.
"There will be moments of frustration, because of results - or personal frustration," said the 63-year-old coach.
"I told the players tomorrow there will come a moment of frustration for many of them because it will be the first time that I have to pick one as a starter and the other goes to the bench and feels frustrated; they have to digest that individually and as a group.
"I'm here to help them, but I can't start a game with 15 players; only 11 can play. I hope each game is difficult for me, because they keep working in the way they are working.
"The day that one lowers his level because of frustration, decisions will be easy for me. I want hard decisions... the team needs to know how to navigate moments of frustration."
Dressing room peace & positive pressure
Los Blancos have failed to win a major trophy for two seasons, and in the previous campaign a dressing room squabble between Aurelien Tchouameni and Fede Valverde ended up with the latter being treated in hospital.
However, the Portuguese veteran coach said the players had made it clear to him there was no bad blood between them now.
"I've decided to start from zero... there was no need to speak to Tchouameni... seeing how they're getting on, you can't even imagine what happened last season," said Mourinho.
"They practically told me there was no need to speak about it, that I didn't have to try and have an influence to bring peace.
"From what I've seen, it's not even about peace, it's normality, friendship, and it's like nothing happened."
Mourinho said he did not feel pressure ahead of his second Madrid debut at the helm.
"I wouldn't call it pressure, I'd call it adrenaline. It's a positive feeling," added Mourinho. "The day I don’t feel it, something's not right."
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