The country music icons will preview their upcoming 'Brothers of the Sun' tour with a special performance at the awards gala, while The Voice's Blake Shelton will share the stage with Lionel Richie for 'You Are'.
Rascal Flatts will team with Hollywood legend Steve Martin for a version of their hit 'Banjo'. Martin recently released a blue grass album and has toured with the Steep Canyon Rangers.
The final duet sees Toby Keith and special surprise guests singing his top ten country hit 'Red Solo Cup'.
Brad Paisley, Kelly Clarkson, Martina McBride, Lady Antebellum, Miranda Lambert, and Jason Aldean are to perform on the ACMs as well.
Taylor Swift, Beth Behrs and Hunter Hayes will be on hand to present.
Shelton and Reba McEntire host the 47th annual Academy of Country Music Awards, airing from Las Vegas on Sunday, April 1, 2012 at 8/7c on CBS.
> ACM Awards 2012 - Nominees in full
> Academy of Country Music Awards to stay on CBS until 2021
Watch Toby Keith's 'Red Solo Cup' music video below: