Underwood is the most decorated artist in CMT Music Awards history with 23 wins.
Ingrid Andress will also make her CMT main stage debut in a world premiere performance with J.P. Saxe.
Brothers Osborne will team with Dierks Bentley on the show, while Guyton will duet with soul queen Gladys Knight.
Thirteen artists in the shortlist are CMT Music Awards nominees for the first time.
Other victors at the Nashville event included Kane Brown, the Zac Brown Band and Ashley McBryde.
Little Big Town played hosts at the event and they triumphed in the Group Video Of The Year category for ‘When Someone Stops Loving You’.
Kelsea Ballerini, Luke Bryan, Kelly Clarkson, Sam Hunt and Blake Shelton are also slated to take to the stage.