Libero says the Portuguese boss is already plotting a return to former club Inter Milan at the end of the season.
His agent, Jorge Mendes, is understood to have initiated contact with club bosses as he tries to manoeuvre a way to get his client the job he wants.
Mourinho has been out of work since being sacked by Manchester United in December.
Reports in Italy suggest that Luciano Spalletti has lost the dressing room at the San Siro after their title bid faded away.
He is now facing a fight to secure Champions League football next season and could face the sack if they miss out, leading to Mendes and Mourinho making their move.