"When Keith Urban calls your phone on FaceTime, you never really get over that. Or at least I don't," Guyton tells PEOPLE with a smile

Mickey Guyton will officially become the first Black solo female artist to host the Academy of Country Music Awards on Sunday night — and her co-host Keith Urban is stoked!

Chatting with People (the TV Show!) this week, the stars opened up about their time performing her smash hit song "What Are You Gonna Tell Her?" at the big show last year.

At the 55th Annual ACM Awards on Sept. 16, Guyton, 37, passionately belted the song as Urban, 53, played the piano in the background.

Reminiscing on the experience, Urban told the host, "We got into rehearsals for that song, I don't really play piano so I was kinda freaked out a bit, but she was great. [But] she made it super easy."

That's when Guyton chimed in, joking, "A lot a bit. I turned around and he goes like this and his hands were shaking ... I'm like, 'What?'"

Check out PEOPLE's full ACM Awards coverage to get the latest news on one of country music's biggest nights.

Mickey Guyton, Keith Urban
Mickey Guyton, Keith Urban
| Credit: Jason Kempin/Getty; Dia Dipasupil/Getty

But for Urban, last year's show-stopping collaboration has made him all the more excited to co-host the big event alongside his fellow country star.

"The idea of doing it with Mickey was so natural for me because we played together on the show last year and we just hit it off," he said while guesting on People (the TV Show!).

And the songstress remembers the moment Urban called her about their new gig for the first time like it was yesterday.

In a sweet clip of their recent FaceTime call, she responded to his invitation, "Yes! Do I have a pulse?"

She later explained, "I knew it was happening, but it doesn't matter. When Keith Urban calls your phone on FaceTime, you never really get over that. Or at least I don't."

The 56th Annual ACM Awards are jam-packed with a star-studded list of exciting acts.

Dierks Bentley will perform U2's "Pride (In the Name of Love)" alongside husband and wife duo, The War and Treaty.

Additional performances include Brothers Osborne with "I'm Not For Everyone," Kenny Chesney will deliver "Knowing You," Eric Church will sing "Bunch of Nothing," Luke Combs will perform "Forever After All," Dan + Shay will hit the stage for "Glad You Exist," Alan Jackson will give "You'll Always Be My Baby" — plus, Chris Young and Kane Brown will perform their duet "Famous Friends."

Guyton will deliver her tune "Hold On" and Urban is also set to show off his skills.

The 2021 ACM Awards will air live from Nashville on Sunday from 8 to 11 p.m. EST on CBS and Paramount+.