The single-electron transfer living radical polymerization (SET-LRP) of water-soluble monomers, N,N-dimethylacrylamide (DMA) and N-isopropylacrylamide (NIPAM), initiated with 2-methylchloropropionate (MCP) in dipolar aprotic and protic solvents is reported. The radical polymerization of acrylamides is characterized by higher rate constants of propagation and bimolecular termination than acrylates. Therefore, the addition of CuCl2 is required to mediate deactivation in the early stages of the reaction. Through the use of Cu(0)-wire/Me-6-TREN catalysis, conditions were optimized to minimize the amount of externally added CuCl2 required to maintain a linear evolution of molecular weight and narrow molecular weight distribution. By using less CuCl2 additive, the amount of soluble copper species that must ultimately be removed from the reaction mixture is reduced. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1752-1763, 2010