Using a commercially available Umemoto's reagent, the metal-free trifluoromethylation of nitroalkanes is now possible. This method provides a general, high-yielding synthesis of α-(trifluoromethyl)nitroalkanes. The quaternary α-(trifluoromethyl)nitroalkanes obtained from this transformation can be elaborated to a variety of complex nitrogen-containing molecules, including α-(trifluoromethyl)amines.