Dylan Scott, Caylee Hammack, and Runaway June, plus DJ Rock, will all guest on the twice-postponed tour.
The ceremony, which honors the best in country music, broadcasts live from Nashville on April 18.
The country artist paid tribute to Patsy Cline, who made the song famous in 1961.
Country stars Gary Allan, Jordan Davis, Caylee Hammack and Josh Turner will play showcase events.
The collaborative single comes ahead of Hammack’s debut album, ‘If It Wasn’t For You.’
The album had been scheduled by Capitol Nashville for 24 April. It will now be out on 7 August with the tour starting on 10 July.
The artist spent the first 32 years of her peerless career at the label group, at Mercury and then MCA.
The success follows the recent conclusion of Bentley's 55-city 'Burning Man Tour.'