Mourinho spent four years at Camp Nou between 1996 and 2000, during which time he got a chance to work with Luis Enrique, who was one of the key players in the Blaugrana line-up under both Bobby Robson and the Englishman's successor, Louis van Gaal.
Mourinho ran into the new Barca boss at a coaching conference in Switzerland this week and revealed that he wished the former midfield ace all the best.
"He was not only one of my favourites as a player during my time at Barcelona but also as a person," the Chelsea manager told reporters on Thursday.
"I have a special fondness and admiration for him. He could play midfield, right wing, left wing, No.10, centre-forward, right-back, left-back - he was even capable of playing in goal.
"Today [Thursday] was the first the first time I've seen him since I left the club in 2000. I asked him if he was enjoying coaching and he said 'Yes'.
"I want him to be happy and I hope he does very well."
Mourinho spent three years in charge of Barca's bitter rivals Madrid before returning to Chelsea last summer.
Luis Enrique, meanwhile, succeeded Gerardo Martino as Blaugrana coach this summer after a productive season in charge of Celta.