The festival, which will start from December 7, is directed by Selvaggia Velo. It is the only festival in Italy entirely devoted to Indian cinema.
Bachchan, 70, will present some of his films including "Deewaar", "Sholay", "Black" and a documentary on his life at the festival, said a statement.
The event will take place at Cinema Odeon, in Florence, under the Patronage of the Embassy of India and the Italy-India association.
A restored version of India's very first film 'Raja Harishchandra' by Dadasaheb Phalke will also be shown at the festival in collaboration with the National Film Archive of India.