The bulk industrial chemical 2-bromo-3,3,3-trifluoropropene (BTP) was first employed as a coupling partner in photocatalytic defluorinative reactions with N-aryl amino acids. Photoredox activation of the C(sp2)-Br bond of the resultant 2-bromo-1,1-difluoroalkenes generates gem-difluoro vinyl radicals for further radical cyclization. Various 4-(difluoromethylidene)-tetrahydroquinolines were assembled in good yields by combining two photoredox cycles with a single photocatalyst.