Mickey Guyton and the Black Pumas Show Off Their Chemistry in New CMT Crossroads Edition

Mickey Guyton and the Black Pumas sizzled on the CMT Awards show back in April, but that was just their warmup. On Wednesday, the country artist and the psychedelic soul band will be synergizing for an entire hour in the latest installment of the CMT Crossroads series.

Before the taping of the show in late April at a Nashville-area venue, Guyton explained that she jumped at the chance to collaborate with the Austin-based duo, made up of lead vocalist Eric Burton and guitarist Adrian Quesada, when CMT came calling. The band first popped on the radar of her husband, Grant Savoy, in 2020 when both Guyton and the band were nominated for Grammys.

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"He was just listening to them all the time," Guyton, 38, told PEOPLE, "so we started listening to the whole catalog, and I just grew to love them, too."

Guyton and the Black Pumas first performed together at an Arkansas concert about a year ago, and then a national audience got to experience the chemistry between Guyton and Burton on the CMTs when they collaborated on the Black Pumas' hit "Colors."

"It feels almost familial," Burton, 32, told PEOPLE about his relationship with Guyton. "When Mickey stepped in, it felt like she could have been a part of the band."

Catherine Powell Mickey Guyton and the Black Pumas

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Their "Crossroads" episode is split almost evenly between each act's music. The first half features Guyton's "Lay It on Me" and "Black Like Me," both from her 2021 debut album Remember Her Name; her first single, 2015's "Better Than You Left Me"; and a brand-new song, "I Still Pray," which she co-wrote with Florida Georgia Line's Tyler Hubbard, as well as songwriters Steph Jones and Ryan Daley. (Look for "I Still Pray" on Guyton's next album, which she expects to be out later this year.)

Guyton said rehearsals had already given her the thrill of hearing Burton sing her music. "They're roots, blues, and folk, and to hear him interpret it, you can hear the soul in the music," she said. "I always knew I had soul, but to hear it come from somebody else, you can hear it in my music more, which is really cool."

For the second half of the show, Burton and Quesada take over the setlist, and it includes a cover of Neil Young's classic "Heart of Gold," as well as "Fire," "Oct 33" and Confines" — all tracks on the Black Pumas' 2019 self-titled debut album. The show closes with a joyful reprise of "Colors."

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For Quesada, the most challenging part of the collaboration was simply "cramming a lot into a couple of short rehearsals. We're pulling it off, and it's feeling good. But it was definitely diving into the deep end."

And what was the most fun part?

Burton fielded that question: "Being able to hobnob with Mickey Guyton."

CMT Crossroads: Black Pumas & Mickey Guyton airs at 10 p.m. ET/9 p.m. CT Wednesday on CMT. An encore will air on CMT immediately afterward at 11 p.m. ET/10 p.m. The show also will air on MTV Live at these times: noon ET/11 a.m. Sunday; and 5 p.m. ET/4 p.m. CT and 8 p.m. ET/7 p.m. CT on June 23.