The awards ceremony will air from the Bridgestone Arena in Nashville, and will also feature songs from Darius Rucker, Florida Georgia Line and Lady Antebellum.
Previously announced performers include Taylor Swift, Miranda Lambert's group Pistol Annies, Hunter Hayes and Luke Bryan.
Kristen Bell is returning as host for the second year in a row, and she will be joined by co-host Aldean.
Fans can still vote for this year's CMT Music Awards on the organisation's website through to June 2.
CMT airs the annual ceremony on June 5 at 8pm ET/PT.
Watch Carrie Underwood's 'Good Girl' music video below: