The Hollywood stars and longtime friends will make their debuts at the country music Mecca during a star-studded event at the venue, reported Contactmusic.
Duvall, 84, is to serve as the guest announcer, and will also perform the song Cheyenne from his new drama "Wild Horses", which the actor wrote and directed.
Meanwhile, Thornton will be joined by his band the Boxmasters to play hits from their latest album, Somewhere Down the Road.
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