The campaign, created by Cardiff-based communications agency Stills, launches on November 16 with a series of 48- and 4-sheets in various locations throughout the region, including bus backs and sides.
Each DJ is transformed into a cartoon superhero, illustrated in a retro comic style and collectively forming a "superhero super group".
The line up of DJs includes Pritchard and Dainton from 'Dirty Sanchez', Goldie Lookin Chain's Rhys and Eggsy and former Stereophonics drummer Stuart Cable.
The campaign was designed to capture the irreverent and tongue-in-cheek tone of Xfm South Wales.
On November 29, closer to the launch of the South Wales station, presenters and staff will be hosting their own superhero tour where they will be exploring their transmission area dressed as superheroes.
Lisa Fairclough, marketing manager at Xfm South Wales, said: "The superhero concept promotes the idea that Xfm is no ordinary radio station. The strong visuals reflect the big personalities that we will have on-air and demonstrate the impact the Xfm South Wales will have in the local marketplace."
GCap Media was awarded the licence for Xfm South Wales by Ofcom in May. It will broadcast from the same studios as GCap's Cardiff station Red Dragon.