The Saturdays singer has been no stranger to showing off her close bond with the 32-year-old on Instagram in recent weeks.
But, the 30-year-old made a very forward suggestion during the duo’s most recent show.
The star had been announcing the name of the artist and track as a song reached its end, when she made the hilarious suggestion.
“Demi Lovato, Tell Me You Love Me,” she said, before teasingly adding: “Go on Matt.”
But, the married radio DJ presenter, who wed Bryony Emmett back in 2013, soon hit back at the cheeky request.
“No,” he exclaimed, before quickly moving the light-hearted conversation on by wishing listeners a good afternoon.
During the show, Matt quizzed the star about what her most embarrassing moment on TV was.
Reminiscing about a time she starred on The Saturday Show, she explained that she had been in a cage with a number of other children for a competition.
She went on to add: “Anyway, you had to go wild and I was going wild, of course, so my number got called out and then we had to blow up a balloon as fast as possible and if you could blow it up in time you could meet Justin [Timberlake].”
Admitting that she hadn’t succeeded in her task, the BBC Radio 1 favourite went onto express her sadness that she hadn’t managed to get to meet the American singer-songwriter.
It came just hours after Mollie’s rumoured romance with AJ Pritchard appeared to be pushed out of the picture for good.
The dance duo first sparked speculation that they could be more than friends during the BBC One show last year.
But, Mollie was romantically linked to England cricketer Stuart Broad earlier this month after The Sun reported that they could have been going on dates together.
And while the pair are yet to comment on their supposed relationship, Mollie and Stuart were hit by a huge engagement bombshell this weekend.
The shock move saw odds on the pair tying the knot this year being slashed to 4-1.
Speaking to Express.co.uk, Coral’s Harry Aitkenhead said: “Mollie has remained tight-lipped over the rumours of a romance with Stuart, but we think the pair are definitely together and have seen a lot of people even backing them to get engaged this year.”