At ambient temperature, deprotonated sulfoximines react with 1-trifluoromethylalkenes to provide either N- or C-gem-difluoroalkenylated products. The reaction site depends upon the N substituent of the starting material. The optimal conditions involve the use of a superbasic system NaOH in dimethyl sulfoxide. The reactions are characterized by a broad substrate scope and medium to high yields. Scale-up experiments of both the N- and C-gem-difluoroalkenylations proceeded well. Treatment of a N-difluoroallyl sulfoximine with an aryl thiol under dioxygen afforded the corresponding oxygenated addition product.