A new photoinitiating system for living cationic polymerization of vinyl ethers is reported. In the current approach, visible-light irradiation of dimanganese decacarbonyl (Mn-2(CO)(10)) in the presence of an alkyl bromide results in the formation of carbon-centered radicals. The photochemically generated radicals were then oxidized by diphenyliodonium ions to the corresponding cations. These cations can add vinyl ether monomers, which are then rapidly deactivated by the bromide anions to give a-halide functional end groups. Poly(vinyl ether) chains are then grown through successive photoinduced radical oxidation/addition/deactivation (PROAD) in a controlled manner. The living nature of the system is evaluated through kinetics studies and block copolymer formation.