A visible-light-mediated, haloalkyl-radical-initiated, three-component olefin difunctionalization is reported. The application of haloalkyl radicals generated via halogen atom abstraction by α-aminoalkyl radicals has been demonstrated for accessing a new halogenated chemical space. Overall, the alkylcarbofunctionalization of styrenes was accomplished by employing them as (poly)haloalkyl radical acceptors and subsequent C-C bond formation with quinoxalinones.