S-Monofluoromethyl phosphorothioates represent an important class of organofluorine compounds and are reported here for the first time. A series of S-monofluoromethyl phosphorothioates are conveniently synthesized from different PV-H compounds and PhSO2SCH2F under mild conditions. The method is compatible with common functional groups and provides potential opportunities to synthesize new bioactive molecules for medicinal chemistry.