Facilitated by an electron donor-acceptor (EDA) complex, an efficient β-trifluoromethylation and perfluoroalkylation of enamides with Togni reagent or perfluoroalkyl iodides is presented under transition-metal-free, photocatalyst-free and mild reaction conditions. Notably, using this photocatalyst-free strategy, direct trifluoromethylation and perfluoroalkylation of quinoxalin-2(1H)-one derivatives was also achieved via a photoactive electron donor-acceptor complex.