A 1,3-sulfonyl migration of difluorovinyl sulfonates initiated by a catalytic amount of silver fluoride is presented. α,α-Difluoro-β-ketosulfones were successfully prepared in excellent yields. This method features high chemoselectivity, good functional group tolerance, high atom economy, and mild, environmentally benign reaction conditions. Furthermore, mechanistic experiments indicate that this migration proceeds in an intermolecular pathway and the corresponding sulfinates are possible intermediates.