The actress will don a catsuit to play Samuel L. Jackson's sidekick in Joss Whedon's Marvel superhero ensemble.
This three-disc set will feature all 24 episodes from the latest season.
The network's season kicks off on September 15 with Survivor: Nicaragua.
The actress/singer will appear as a women's self-help author.
Carter Bays and Craig Thomas' new pilot will be set in Pittsburgh.
The CBS hit Monday night comedy was handed a sixth season order.
Kim Kardashian, Kendra Wilkinson, Heidi Montag and Spencer Pratt are set to play versions of themselves on the CBS sitcom.
The talk-show host will star as himself on the CBS series.