Jennifer Nettles Gathers John Legend, Hunter Hayes for CMT Music Awards

Musicians Will Perform "All of Me" on Wednesday (June 4) in Nashville

Jennifer Nettles bursts into singing “Reunited” when her CMT Music Awards performance with John Legend comes up in conversation.

The singers bonded as panelists on ABC’s Duets in 2012, and before that, they met as performers at President Obama’s inauguration in 2009. And now they are indeed reuniting Wednesday (June 4) in Nashville for a duet version of Legend’s smash hit, “All of Me.”

The 2014 CMT Music Awards will air live at 8 p.m. ET.

“We’re similar, energetically-speaking,” Nettles said prior to her solo debut at the Grand Ole Opry on Tuesday night. “He’s a nice, sweet friend in the business.”

Asked why “All of Me” grabbed her, she explained, “It’s such a beautifully crafted, well-written song. It combines both beautiful imagery and, at the same time, has wonderful conversational moments, too. … And then there are moments like, ’Love your curves and all your edges/All your perfect imperfections.’ Are you kidding me?! Obviously, he just got married, so the song was inspired by his love and by his relationship.”

She continued, “The song is inspired, and that is what I like about it. You can tell. It’s not just storytelling. It is inspired from a sweet, sweet place within him. … Musically and melodically, it’s so beautiful. I love the fact that it’s a piano ballad and it’s at the top of the charts. It’s been a long time since that’s happened, and I would love to see it happen more and more.”

Nettles and Legend will be accompanied by Hunter Hayes, who wrote a guitar arrangement of the song specifically for the CMT Music Awards.

Asked if she’s gotten to know Hayes over the years, she replied, “I have not, and I am looking forward to that because I think that he is super, super-talented. Clearly, he’s a multi-instrumentalist and he is a great writer, not to mention a singer and a cutie. But everybody says ’singer’ and ’cutie’ first. The other part is what really interests me. I mean, not that (the more familiar part) doesn’t — but everybody sees that. I really respect his talents and his gifts as a musician as well as a front person. So, yeah, I’ll be excited to get to work with him.”

As for Hayes’ arrangement, Nettles said, “He sounds great, and I think he does a wonderful homage to the song while making it very much ’him.’ It sounds like his guitar work, so that’s cool.”

The Sugarland vocalist acknowledged the pressure that most artists might feel about being put in the position of rearranging a No. 1 hit to be played on another instrument and then performing it with the original artist on live television. That doesn’t appear to be a burden for Hayes, though.

“You know what? He’s young,” Nettles said with a smile. “When you’re young, you don’t worry about stuff like that. You’re like, ’Yeah, I’ll do it!”

Check out videos, photos and more from the 2014 CMT Music Awards.