"Aquaman" also stars former Miss Universe Denise Quinones as Rachel Starling, a U.S. Navy pilot and McCaffery's love interest, Zap2It.com reported.
While Will Toale had been set to play A.C. Curry in the "Smallville" spinoff, The CW changed course and cast soap star Justin Hartley in the twentysomething role.
The Hollywood Reporter, citing sources, said CBS Corp. President-Chief Executive Officer Leslie Moonves was a major reason the "Aquaman" part was recast.
Rhames starred in USA's "Kojak" revival last year.
He will reprise his role as Luther Stickell in the movie "Mission: Impossible III" later this year.