The cop thriller stars English actor Theo James as a young officer who rises through the ranks from detective to police commissioner.
Annable will play Kat O'Connor, an Assistant District Attorney who prosecutes the squad's criminal cases, Deadline reports.
The 27-year-old Cloverfield actress also recently signed up to star in Cinemax drama Banshee, from True Blood's Alan Ball.
Chi McBride (Human Target) and Holt McCallany (Lights Out) will also star in Golden Boy, which will air on CBS in 2013.
Ryan Phillippe was previously attached to the lead role, but later dropped out of the project and was replaced by James.
> Bones creator Hart Hanson developing new crime drama for CBS
> Odette Annable joins House cast as regular