"I'm Jess!" Glynne replied, before admitting she was feeling nervous up on the stage.
"You know what, when you're all sat there, it's mad scary. Whoever does this, I'm really proud. Big up."
Sebastian had a big fan moment with the star, telling her he uses her as "an example" to his contestants.
"When you're on the radio, you sound like nobody else. I love your voice," he gushed.
Glynne wasn't the only familiar face to pop up during last night's episode of The Voice.
Nathan Foley — a former children's entertainer who was part of the original Hi-5 line-up — performed Footloose, turning Goodrem and George's chairs in the process.
Both Goodrem and Sebastian recognised Foley from Hi-5, with the Australian Idol winner gutted he didn't turn his chair.
"It's funny because singers in this country always knew that Nathan, like, is a beast singer. And I am kicking myself for not turning, I really am," Sebastian said.