Imperioli has been cast in the action drama series as an "ex-New York transplant who's become a surfer/confidential informant" for Steve McGarrett (Alex O'Loughlin), according to executive producer Peter M Lenkov.
His character Odell Martin is a reformed ex-con who keeps tabs on the criminal underworld in his barbershop.
Imperioli, 48, will appear in at least two episodes of Hawaii Five-0 next year, reported Entertainment Weekly.
The actor is the latest name announced as a guest star for the CBS series, with NCIS's Sarah Jane Morris and singer Frankie Valli also slated for appearances.