Radical defluorinative functionalization of α-trifluoromethyl styrenes represents an effective way toward gem-difluoroalkenes. There are general interests in developing novel synthetic protocols for defluorinative functionalization with various types of radicals. However, reports on the preparation of gem-difluoro allylsulfones via an S-centered radical pathway are limited. Herein, we developed a photo/nickel dual-catalyzed defluorinative sulfonylation that rapidly and reliably synthesizes gem-difluoro allylsulfones. The merit of this protocol is exhibited by its mild conditions and wide scope, thus providing a novel strategy for the sulfonyl radical participating in radical defluorinative coupling.