With a roster that included Miranda Lambert, Jason Aldean, Luke Bryan, and a Glen Campbell tribute from Blake Shelton, Keith Urban, Dierks Bentley and Toby Keith, country newcomer Cam stole the show with a big assist from Alicia Keys and Little Big Town's smash hit, "Girl Crush."
Cam and Alicia hit the stage at the historic Ryman Theater in Nashville, paying tribute to the band at the ACM Honors ceremony. The special aired on CBS on Friday, Sept. 9.
WATCH: Behind the Scenes of Cam's Stunning 'Burning House' Video
Only ET was backstage with Cam before the big moment, where she gushed over rehearsing with the "In Common" singer.
"My first time meeting her was in rehearsal and I genuinely made a face like, 'Oh, my f**king God!'" she adorably confessed. "She's so, so good and is in such a great place."
Inside The Ryman later that night, while seated at a piano, Alicia's powerhouse vocals prompted the entire theater to erupt into mid-performance cheers not once, but twice.
"She's mastered music and life," Cam mused earlier about her duet partner. "She is incredible to be around!"
WATCH: Alicia Keys and Miley Cyrus Prove Their Power in 'The Voice' Season 11 Preview
Little Big Town was honored with the Crystal Milestone Award for their double platinum song, which spent 13 consecutive weeks atop the Billboard Hot Country Songs chart and scored the band its 10th nomination in the ACM Vocal Group of the Year category.
"It's made just a huge massive dent in the landscape. It is just so cool that no one will ever forget that song," said Cam. "It's a lot of high stakes, and they are sitting right there watching while we sing it, so fingers-crossed we will do them proud." (Safe to say, they did!)
For more behind-the-scenes action from Nashville, see the video below.
WATCH: EXCLUSIVE: All the Behind-the-Scenes Fun You Didn’t See at the ACM Honors