The Voice UK coaches will team up for an exclusive duet for BBC Radio 2 and perform during Chris Evans's hour-long broadcast from 6pm.
The show will air live from The 100 Club in London on May 10, where the pair will perform their duet for the first time.
"Tom Jones and Jessie J are a fantastic addition to 2Day," said Helen Thomas, 2Day executive producer. "We have some amazing live music and entertainment throughout the day and listeners are in for a real treat."
Other acts confirmed for Radio 2's 2Day include Keane, Paloma Faith, Damon Albarn and T'Pau lead singer Carol Decker, who will perform the group's hit 'China In Your Hand'.
Zoe Ball, Dermot O'Leary, Simon Mayo, Ken Bruce, Jo Whiley and Sir Terry Wogan will all host an hour throughout the day's schedule.
2Day will see the departure of the usual Radio 2 schedule for one day only, to allow the network to showcase the variety of content that they have to offer.
> Jessie J: 'Tom Jones collaboration will happen soon'
Watch the music video for Jessie J's new single 'LaserLight' below: