Woods will play Patrick "Sully" Sullivan on the show.
"Living in his hometown of South Boston, Sully has a very complicated history with the Donovan family. The series marks a return to television for Woods, who last starred as the title character in the CBS drama series 'Shark,'" the cable network said in a news release Tuesday.
Woods' film credits include "Once Upon a Time in America," "Against All Odds," "Casino," "True Believer," "The Virgin Suicides," "Pretty Persuasion," "Kung Fu Panda 2," "Straw Dogs" and "Ghosts of Mississippi." He also won Emmy Awards for his work in "Promise" and "My Name Is Bill W."
Liev Schreiber plays Ray Donovan, a man who makes the problems of LA's celebrities, superstar athletes and business moguls disappear, Showtime said in a synopsis. The series co-stars Jon Voight, Elliott Gould and Eddie Marsan.