The 'All Summer Long' star will join previously-announced performers including Miranda Lambert, Taylor Swift and Lady Antebellum at the event next month.
Other stars who will take to the stage include Carrie Underwood, Brad Paisley, Kenny Chesney, Blake Shelton, Sugarland, Keith Urban and Rascal Flatts, while Kelly Clarkson and Jason Aldean will perform a duet.
Sara Evans has also been added to the presenter lineup for the Nashville event. Other presenters include Martina McBride, Ty Pennington, Luke Bryan and Tim McGraw.
Lambert will enter the evening with the most nominations, including recognition in the 'Entertainer Of The Year', 'Female Vocalist Of The Year' and 'Album Of The Year' fields.
The 44th annual CMA Awards air live on November 10 from 8pm ET on ABC.
> CMA Awards 2010: The Nominees