The 30 Rock star will portray Harold, a mobster who is kidnapped and held hostage by two troubled brothers, in director Daniel Sullivan's next project, an adaptation of Lyle Kessler's 1983 play.
Orphans was last staged Off-Broadway in 1985. It was also turned into a 1987 movie starring Albert Finney as the lead character.
Baldwin is no stranger to the New York theatre community - he previously starred in the Off-Broadway production of Entertaining Mr. Sloane in 2006 and in 2004 took a bow on Broadway in Twentieth Century.
He also garnered a Tony Award for best actor in 1992 for his turn in A Streetcar Named Desire.
The actor recently revealed he is developing a new Broadway musical, in which he plans to star as a wannabe song and dance man.