An oxidative azido-difluoromethylthiolation of alkenes by employing TMSN3 as the azide source and PhSO2SCF2H as the difluoromethylthiolation reagent is reported. The present method is characterized by good functional group tolerance, broad substrate scope, and short reaction time, thereby providing an efficient access to synthetically useful β-difluoromethylthiolated azides. Mechanistic studies indicate a radical pathway involved in the reaction.