Visible-light-induced [3+2] cyclization of vinyl azides with perfluoroalkyl-substituted imidoyl sulfoxonium ylides has been developed for the first time. In this transformation, perfluoroalkyl-substituted imidoyl sulfoxonium ylides are firstly employed as a carbon radical precursor under visible light irradiation, providing a new and efficient method for the construction of perfluoroalkyl-substituted 1-pyrrolines.