David Harbour, Michael Shannon and Zoe Kazan also are boarding the 1950s-set drama, which revolves around a suburban Connecticut couple whose relationship deteriorates into an endless cycle of squabbling, jealousy and recriminations.
Justin Haythe adapted Richard Yates' acclaimed 1961 novel, which was a finalist for the National Book Award.
Bates will play Mrs. Givings, who sells the couple their home and introduces them to the town. Harbour will play Shep Campbell, a neighbor. Shannon will play the son of Bates' character. And Kazan will play Maureen, secretary of DiCaprio's character, with whom she embarks on an affair.
Scott Rudin, John Hart, Bobby Cohen and Mendes are producing the film, which begins shooting outside New York in June.