Also set to take the stage is Cody Johnson, Kelsea Ballerini, Kenny Chesney, HARDY and more.
The hotly anticipated duet will be released on November 10.
Also set to perform at the Alabama festival is Parker McCollum, Oliver Anthony, Warren Zeiders, Flatland Cavalry and more.
The first acoustic track from the project has been made available everywhere immediately.
The folk-leaning artists have teamed up on-stage twice in recent months.
The prestigious ceremony is due to take place on November 19 in Las Vegas.
