Marsters has been cast as the dangerous terrorist leader Barnabus Greeley for at least three episodes, with the potential for more, SyFy confirmed to TVGuide.com.
The character is described as an unpredictable villain who often finds himself torn by his conflicting motivations, which are driven by moralistic and yet carnal desires.
Best known for his role as punk-goth vampire Spike on Buffy the Vampire Slayer and Angel, Marsters most recently appeared in Without a Trace, Smallville and Torchwood.
Caprica debuts on Syfy on Friday, January 22.
What do you think of the addition of Marsters?