Christina Davidson and Frank Tucci, a couple from New Jersey, were selected to exchange vows on the prize presentation.
"To celebrate the message of the song, McBride and Monahan will perform the duet during a very special moment in the show, when a couple will get married live onstage," the network said in a news release.
The song was written by Monahan and originally released in 2010 on his rock band Train's fifth studio album, "Save Me, San Francisco."
McBride, a country music star, covered the song on her latest album, "Eleven."
The ACM Awards show is to take place Sunday at the MGM Grand Garden Arena.
Celebrity Breakups and divorces of 2014 [PHOTOS]