A simple and efficient method for the synthesis of 2‐trifluoromethyl quinolines by means of visible‐light‐induced radicalcyclization of trifluoroacetimidoylchlorides with alkynes has been developed. This protocol allows the generation of imidoyl radicals by activation of C(sp2)Cl bonds using a photoredox catalyst under mild and environmentally friendly conditions (see scheme).