Perfluoroalkylsulfonyl chlorides and bromides initiate metal catalyzed free radical polymerization of both hydrocarbon and fluorocarbon monomers affording polymers with perfluoroalkyl end groups. In the case of styrene (S) and methyl methacrylate (MMA) with Cu-based catalysts the process affords polymers with a relatively narrow molecular weight distribution and linear dependence of molecular weight on conversion, suggesting that a living radical polymerization mechanism occurs. The orders of reaction in monomer, initiator and catalyst for these polymerizations were determined. In the case of PMMA, the detailed structure of a perfluorobutane chain-end was determined by NMR analysis. Perfluoroalkylsulfonyl chlorides are stable in neutral aqueous media. This permits their use as initators for fluoroolefin polymerizations in H2O. Poly(tetrafluoroethylene-co-hexafluoropropylene) was obtained in go od yield with few ionic end groups. The aqueous fluoroolefin polymerization appears to be catalyzed by metal zero species from the reactor walls.