The Dum Maaro Dum star has teamed up with the actress in hits such as Bunty Aur Babli and Kabhi Alvida Na Kehna.
He told Mumbai Mirror: "Rani is the best co-star I have ever worked with. She's beautiful and is a brilliant actor."
Bachchan will next be seen in a film about the Goan criminal underworld, which also stars Bipasha Basu and Ranu Daggabati.
According to rumours, his real-life wife Aishwarya Rai was first choice for the role of Bachchan's on-screen love interest in the controversial movie.
After the two starred in Yuva together, Mukherjee denied that she was romantically involved with Bachchan, stating that they were just friends.