Direct and selective fluoroarylations of nucleophilic secondary alkylanilines with polyfluoroarenes were first realized through visible-light-induced C-H/C-F couplings with the assistance of bases. Varieties of α-polyfluoroarylanilines were selectively produced with this protocol from polyfluoroarenes and N-alkylanilines, including natural products and pharmaceutical molecule derivatives. Mechanistic studies illustrated base-promoted photochemical C-H cleavage of the α-C-H bonds of alkylanilines to produce the N-α-carbon radical and then radical addition to polyfluoroarenes.