The Italian will take charge of his first Champions League game with the Spanish club when United visit the Ramon Sanchez Pizjuan on Wednesday, having taken over from the sacked Eduardo Berizzo in December.
Up next in La Liga is a trip to Las Palmas on Saturday and, when asked about the difference in challenge between the Canary Islands club and United, Montella highlighted Mourinho.
"Mourinho is more of a winner than any of us," Montella told reporters on Friday. "He's coaching in a way that gets in the mind of the player to get the best out of them.
"I like [Las Palmas coach] Paco Jemez because his team has identity. They always look to play and are organised without the ball.
"They're two different philosophies, but if I wanted to be like either of them it would be for Mourinho's capacity to win, respecting Paco of course, who has a career trajectory more similar to mine."