The married singers are to lead a special tribute to country music legend Willie Nelson with Lady Antebellum and Blake Shelton, as well as perform songs from their new albums.
Carrie Underwood, The Band Perry, Kenny Chesney and Eric Church are also scheduled to take to the stage at the Nashville ceremony.
Miranda Lambert, Kelly Clarkson, Little Big Town, Jason Aldean and Dierks Bentley are on the CMA Awards' all-star line-up as well.
Multiple nominees for the 2012 CMA Awards include Taylor Swift, Church, Lady Antebellum and Toby Keith.
The Country Music Association Awards 2012 - hosted by Brad Paisley and Carrie Underwood - are broadcast on Thursday, November 1 at 8pm ET on ABC.
Listen to Faith Hill's new single 'American Heart' below: