For the unforgettable performance, Underwood turned to her March 2021 album, My Savior, and performed a medley of those gospel hymns.
Belting out a few of iconic gospel classics, including "Amazing Grace," "The Old Rugged Cross" and "How Great Thou Art," Underwood stunned with her spotlight-stealing appearance.
At one point in Underwood's performance, she was joined by CeCe Winans for a duet of "Great Is Thy Faithfulness," which the pair collaborated on for Underwood's recent album.
Dolly Parton introduced the performance in a pre-recorded message, who marveled, "I am so pleased and proud to introduce my dear friend, Carrie Underwood."
"I have always admired Carrie's incredible talent, but I am just as impressed with her personal qualities-- her compassion, kindness, generosity, and, most of all, the powerful faith that we both share," Parton said. "Now, her performance tonight speaks to that faith in a medley from her new gospel hymns album, My Savior, which I know is a true passion project for her."
It was a sweet introduction for one of the night's biggest highlight performances.
ET's Rachel Smith recently spoke with Winans, and the songstress said getting to collaborate with Underwood was like a "divine connection" that resulted after years of watching Underwood's career bloom.
"I met Carrie years ago when she first won American Idol. I heard her on American Idol, of course, she's amazing. But then we both sang at the White House. I think it was Christmas at the White House," Winans recalled. "I got to hear her up close and personal and I was just like, 'Whoa, this girl can really really sing!'"
As for recording their duet of "Great Is Thy Faithfulness," Winans said, "It was fun, because she's amazing."
"I got a chance to go in and kind of just do my part, because she had really had already done hers. And when I finished she changed some things and I just love it," Winans recalled. "It's a beautiful song."