A novel fluoro-xanthate, 2-((4-fluorophenoxycarbonothioyl)thio)ethyl propanoate, was developed and successfully used as a mediator in the photoinduced controlled radical polymerization of more-activated monomers (methyl acrylate (MA), butyl acrylate, and N-isopropylacrylamide) and a less-activated monomer (vinyl acetate (VAc)). The controlled characteristics of the polymerization were demonstrated by the linearly increasing molar mass with conversion, producing polymers with narrow molar mass distributions (1.14–1.37) for MA and VAc. Furthermore, the block copolymer of PMA-b-PVAc was successfully synthesized through chain-extension using PMA as the macro-RAFT agent and VAc as the second monomer.