The pilot, from Jon Feldman, Chris Brancato and Bert Salke, focuses on six former friends and San Francisco cops reunited to solve the murder of another of their chums.
According to The Hollywood Reporter, Montgomery will play a police captain, with Blucas as her ex-husband, a detective.
Peter Horton will direct the pilot.
Credits for Blucas include recent episodes of "Castle" and "Lie to Me," as well as his extended turn as Riley on "Buffy the Vampire Slayer."
A longtime regular on "Without a Trace," Montgomery was also a regular on the short-lived "Glory Days."