The project is based on Nelson Johnson's book, which chronicles the 1920s origins of Atlantic City, N.J. Scorsese will direct from an adaptation by Terrence Winter.
Buscemi plays a cunning businessman who runs a liquor distribution ring at the onset of Prohibition, while Pitt plays a ruthless flunky.
Scottish actress Kelly Macdonald ("Trainspotting") was previously cast as a smart Irish immigrant who married the wrong man to get out of her parents' house.
Pitt, who had a recurring role on "Dawson's Creek," also starred in the feature films "The Dreamers" and "Last Days." He was last in theaters with the home-invasion horror "Funny Games," playing a callous murderer.
Reuters/Hollywood Reporter