Abstract : An unprecedented electrophilic difluoromethylthiolating reagent (MesNHSCF2PO(OEt)2) was designed. Under mild and metal‐free conditions, this new reagent reacted with various nucleophiles, thus offering an efficient and operationally simple tool for the construction of C−SCF2PO(OR)2, N−SCF2PO(OR)2, and S−SCF2PO(OR)2 bonds. Finally, thanks to this new methodology, the synthesis of the non‐stereoidal anti‐inflammatory diflumidone was achieved.