Herein, we disclose a direct and powerful strategy for the synthesis of highly valuable α-trifluoromethylamine and N-trifluoroethylamine derivatives from a visible-light-promoted C,N-selective heteroarylation of N-trifluoroethyl hydroxylamine reagents with quinoxalin-2(1H)-ones under ambient conditions. The chemoselectivity of the process (trifluoroalkylation or N-trifluoroethylamination) can easily be dictated and modulated by a selection of N-trifluoroethyl hydroxylamine substrates. The key to success is the protecting group on the N atom of hydroxylamine reagents, which can control the process of 1,2-H shift of the in situ-generated N-trifluoroethyl radical. Remarkable features of this method include mild conditions, easy operation, high selectivity, and excellent functional group tolerability. More importantly, the trifluoroalkylated products can be readily derivatized into other interesting imidazo-fused heterocycles that would be of great potential for the exploitation of pharmaceutically relevant molecules.