In this report, we develop a new strategy for visible-light-induced, copper-catalyzed three-component difluoroalkyl thiocyanidation of alkenes to construct a series of important difluorothiocyanate compounds. The new approach can also be applied to perfluorothiocyanate compounds, even target molecules containing drug/natural product skeletons. Mechanistic studies provide that the copper complex plays a dual role, as both the photoredox catalyst for electron transfer and the cross-coupling catalyst for C-SCN bond formation.