The couple, who have been together for 15 years, admitted before their audition that they had "very different ideas" on which team they were hoping to join.
Performing A Little Time, Sir Tom was first to turn around, followed by Jessie at the last second.
"I enjoyed that the harmonies you used, they were really interesting, I loved how your voices blended," she told the pair.
Sir Tom added: "I loved everything about, it was really, really good"
But the couple couldn't decide between the pair.
Matt suggested, to surprised looks from the coaches and their friends and family backstage: "Do you wanna flip for it?"
Sueleen explained: “It sounds bad, but you've both got such diffrent backgrounds..."
Luck was on Sir Tom Jones' side as he won the coin toss with heads to become the duo's coach.
Watch [tag]Matt and Sueleen Fletcher[/tag]'s blind audition on The Voice UK below...