alpha,omega(iodo)poly(vinyl chloride)s [alpha,omega-di(iodo)PVCs] with number-average molecular weights ranging from 2100 to 20,000 and weight-average molecular weight/number-average molecular weight ratios ranging from 1.72 to 2.16 were synthesized through the single-electron-transfer/degenerative-chain-transfer mediated living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by sodium dithionite in water at 25-35 degrees C. These alpha,omega-di(iodo)PVCs were used as macroinitiators for the metal-catalyzed living radical block copolymerization of methyl methacrylate to produce poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) block copolymers. By searching various copper derivatives, ligands, and solvents, it has been found that CuCl/tris(2-dimethylaminoethyl)amine in dimethyl sulfoxide at 90 degrees C provides an accelerated method for the synthesis of block copolymers. Poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) block copolymers with number-average molecular weights of 41,000-106,700 were produced by this method in 30-80 min. These reaction times were within the range of induction times exhibited when the same block copolymers were synthesized with CuCl/2,2'-bipyridine in diphenyl ether at 90 degrees C. (c) 2005 Wiley Periodicals, Inc.