Thomas Rhett and Katy Perry Join Forces for 'Where We Started' Duet at the 2022 CMA Awards

Thomas Rhett and Katy Perry perform onstage at The 56th Annual CMA Awards at Bridgestone Arena on November 09, 2022 in Nashville, Tennessee.
Thomas Rhett and Katy Perry perform onstage at The 56th Annual CMA Awards at Bridgestone Arena on November 09, 2022 in Nashville, Tennessee.
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Michael Loccisano/Getty Thomas Rhett and Katy Perry

Thomas Rhett and Katy Perry brought bittersweet feels to country music's biggest night!

At Wednesday's 56th Annual CMA Awards in Nashville, Thomas Rhett and Perry took the stage to perform their collaboration "Where We Started," which was featured on the country singer's latest album with the same name.

Rhett opened the performance, donning a leather jacket and standing in front of a fringe backdrop with clips from the song's music video projected onto it. After the first chorus, Perry joined him onstage, wearing a denim dress paired with fishnet tights, a choker necklace and a black cowboy hat.

Thomas Rhett and Katy Perry attend the 56th Annual Country Music Association Awards at Bridgestone Arena on November 09, 2022 in Nashville, Tennessee.
Thomas Rhett and Katy Perry attend the 56th Annual Country Music Association Awards at Bridgestone Arena on November 09, 2022 in Nashville, Tennessee.

John Shearer/Getty Thomas Rhett and Katy Perry

At the end of the performance, both performers shouted out each other's names and shared a hug.

"Where We Started" served as the title track for the country singer's sixth studio album, which dropped in April. In January, Thomas Rhett, 32, spoke to PEOPLE about the making of the album and getting to work with the "Dark Horse" singer, 38.

RELATED: Alan Jackson to Receive 2022 CMA Lifetime Achievement Award with Star-Studded Tribute Performance

2022 CMA Arrivals
2022 CMA Arrivals

Jason Kempin/Getty Katy Perry

"I don't think we were looking for a collaboration on this song," he said of the song that eventually became the album's title track. "Allison Jones over at the label was like, 'Do you care if I send this to Katy Perry's team?' And I was like, 'Yeah, but I mean, they're not going to respond, but you can send it."

And within 24 hours, Perry was all in.

For more on the 2022 CMA Awards, listen below to our daily podcast PEOPLE Every Day.

"She really put a lot of time and effort into this vocal and it's one of the best," he said of his collaboration with the star. "I mean, she's an incredible singer, but this kind of reminded me of how amazing of a vocalist she is. I just felt like it really came to life.

Check out PEOPLE's full CMA Awards coverage to get the latest news on country's biggest night.

2022 CMA Arrivals
2022 CMA Arrivals

Matt Baron/BEI/Shutterstock Thomas Rhett and Lauren Akins

Later, in February, the "Marry Me" singer said getting to work with the Teenage Dream songstress was a dream come true.

"I've always been such a huge fan of hers, from the time I was 14. Katy Perry was like, the jam and still is," he told PEOPLE. "She heard the song and was like, 'How do I be a part of this?' And I was like, 'I can't believe that you know who I am, first of all. Second of all, are you serious? Because the answer is yes.'"

The stars also bonded over their experience as parents.

RELATED VIDEO: Thomas Rhett Said He Didn't Think Katy Perry Would 'Respond' to a Collab Request but She Did

Thomas Rhett and wife Lauren Akins are parents to daughters Willa Gray, 7, Ada James, 5, Lennon Love, 2, and Lillie Carolina, 11 months, while Perry shares her 2-year-old Daisy Dove with fiancé Orlando Bloom.

"We literally talked about our kids the entire time… how we're raisin' 'em and what we're feeding 'em," he said in Oct. 21 on Audacy's Rob + Holly. "I think that's what you do as a parent these days, you're just like, 'Oh, let me show you this one picture on my phone of my kid that you've never met!'"

The CMA Awards, hosted by Luke Bryan and Peyton Manning, are broadcasting live from Nashville on ABC on Nov. 9 at 8 p.m. ET.