The thriller stars ER's Anthony Edwards as a journalist who finds himself caught up in a global conspiracy when his wife is kidnapped.
Carmen Ejogo (Chaos) will play an FBI agent on the series, with Baker now cast as her superior, FBI Section Chief Terrence Fisk, according to TV Guide.
The 52-year-old actor has appeared on such shows as The Good Wife, Damages, Smash and Political Animals, while his film credits include Sam Raimi's Spider-Man film trilogy and 2008's Revolutionary Road.
Zero Hour - co-created by Prison Break's Paul Scheuring - also stars Scott Michael Foster (The River), Addison Timlin (Californication), Jacinda Barrett (Suits) and Michael Nyqvist (The Girl with the Dragon Tattoo).
The series will premiere on ABC in 2013.
> Dylan Baker lands White Collar role
> Dylan Baker returning to The Good Wife
Watch a trailer for Zero Hour below: