Urban and the show's co-hosts, Brad Paisley and Carrie Underwood, will perform the opening number at the show Wednesday, which airs live on ABC (8 pm. ET).
Underwood, who is nominated for two awards including top female vocalist, will also perform her hit "Mama's Song."
Paisley, who is nominated for three awards, will be vying for a fourth consecutive top male vocalist award. He's up against legend George Strait and Urban.
Other performers for the evening include nine-time nominee Miranda Lambert, who plans to show off her svelte new figure, and Country Strong actress Gwyneth Paltrow, who will be making her live singing debut at the show