Dan+Shay, Kelsea Ballerini and Old Dominion will also perform at the award ceremony, which will be hosted by Underwood and Brad Paisley.
The Country Music Association made the announcement on Friday, Oct. 19 via their official website and social media. More performers will be announced in the coming weeks.
Chris Stapleton leads this year's CMA nominations with seven nominations. The "Tennessee Whiskey" singer is nominated for Entertainer of the Year, Male Vocalist of the Year, Single of the Year and Song of the Year (for "Broken Halos) and Album of the Year (for From A Room: Vol 2).
Miranda Lambert, Dan+Shay, Thomas Rhett, Jason Aldean and Urban follow Stapleton with four nominations each.
The 2018 CMA Awards will air Nov. 14 on ABC at 7 p.m CT.