Herein, we report a metal-free light-induced three-component reaction for the synthesis of polychloroalkyl-substituted quinoxalin-2(1H)-ones using commercially available alkenes, polyhalo alkanes, and quinoxalin-2(1H)-ones. Preliminary mechanistic studies suggested the generation of radical intermediates via an EDA-complex, single electron transfer, or halogen atom transfer pathway. Under mild reaction conditions, various alkenes and quinoxalin-2(1H)-ones containing different functional groups are compatible, providing the corresponding polychloroalkyl-substituted quinoxalin-2(1H)-ones in moderate to good yields.