The actor, Oscar-nominated for Revolutionary Road, will play a Treasury Department agent striving to control bootlegging in Prohibition era New Jersey.
Steve Buscemi and Michael Pitt are already among the cast as liquor racketeer Nucky Johnson and low-level enforcer Jimmy Darmody respectively. Vincent Piazza will portray Sicilian mobster Lucky Luciano.
Based on Nelson Johnson's book, Boardwalk Empire will chart the rise of organised crime in Atlantic City in the early 20th century. Scorsese will direct the pilot and executive produce from a script by Terrence Winter (The Sopranos).