A DABCO-mediated electrophilic α-trifluoromethylthiolation of α,β-unsaturated carbonyl compounds comprising no β-substituents has been achieved using N-trifluoromethylthio-dibenzenesulfonimide as the SCF 3 source. The direct trifluoromethylthiolation provides the corresponding α-trifluoromethylthio-α,β-unsaturated carbonyl products in good yields (up to 88%). Furthermore, the vinyl group in the α-trifluoromethylthioα,β-unsaturated carbonyl product was successfully transformed into diverse functional groups in good to excellent yields (70−95%) by reactions such as epoxidation, aziridination, hydrocyanation, and hydrogenation.