Introducing distinctive functional groups to expand the structural diversity and improve the intrinsic properties of parent molecules has been an essential pursuit in organic chemistry. By using perfluoroalkyl halide (PFAH) as a nontraditional, readily available, ideal 1,2-difluoroalkenyl coupling partner, a defluorinative cyclization reaction of enamides for the construction of fluoroalkenyl oxazoles is first developed. The selective and controllable two-fold cleavage of vicinal C(sp