"I was like, 'How do you look that beautiful, no makeup?'" she told ET's Sophie Schillaci. "It was like they were going to the grocery store or something, popped in the car and said 'Let's sing the song.' I'm jealous."
Jason Aldean hit the carpet with his wife, Brittany Kerr, while "Buy Me a Boat" singer Chris Janson and wife Kelly Lynn shared a smooch for the cameras.
Lady Antebellum's Charles Kelley and wife Cassie McConnell posed for a snapshot with Nashvillestar Clara Bown and fiancé Robert Young.
Racecar driver Danica Patrick also attended the show with husband and fellow racer, Ricky Stenhouse, Jr.
Meanwhile, Thomas Rhett -- who snagged Male Video of the Year for "Die a Happy Man" -- brought his lovely wife, Lauren Gregory. Rhett dished to ET about how his better half helps him get ready for awards shows.
"Usually my stylist will pull about 10 different suits and she'll pick her favorite and that's what I'll wear," he admitted.
Other couples on the CMT carpet included Agent Carter star Chad Michael Murray and his wife, Sarah Roemer, as well as Florida Georgia Line rockers Brian Kelly and Tyler Hubbard with their wives, Brittney Marie Cole and Hayley Stommel.
"They keep us straight, keep us loving life and on the road together it's amazing," Hubbard gushed to ET of FGL's significant others. "We love having them out getting to do what we love. It's a beautiful thing for real."
See ET's exclusive footage from the CMT Awards below.