The generation of carbon-centered radicals from alkyl bromides through an oxidative quenching pathway using perylene as an organic visible-light photocatalyst is described. This methodology is used to initiate the radical polymerization of methyl methacrylate and other functionalized vinyl monomers. The polymers possess bromide chain-end groups that can be used to reinitiate polymerization to produce block copolymers. Control over the polymerization propagation can be achieved through pulsed light sequences while the ability to use natural sunlight to promote carboncarbon bond formation produces polymers with dispersity as low as 1.29.