A newly developed CF₃SO₂Na-based trifluoromethylation of secondary amines has been disclosed, and the method has been successfully extended to the configuration of perfluoroalkyl amines using R_fSO₂Na, complementing the established synthesis strategy of trifluoromethyl amines. Advantages of the method include good functional group tolerance, mild conditions, and inexpensive or easy-to-handle materials. Mechanistic probes indicate that the thiocarbonyl fluoride formed in situ is the key intermediate in the reaction.