alpha,omega-Di(iodo)poly(vinyl chloride)s, with number-average molecular weights ranging from 2100 to 29,500 and molecular weight distributions (weight-average molecular weight/number-average molecular weight) ranging from 1.74 to 2.16, were prepared by the previously reported 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)poly(vinyl chloride) macroinitiators were used for the synthesis of poly(methyl methaerylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) (PMMA-b-PVC-b-PMMA) block copolymers via the metal-catalyzed living radical block copolymerization of methyl methacrylate. In this article, we report the effects of various ligands on the rate of block copolymerization mediated by Cu(0) in dimethyl sulfoxide (DMSO). The block copolymerization catalyzed by Cu(0)/tris(2-dimethylaminoethyl)amine in DMSO at 90 degrees C yielded block copolymers in less than 15 min, whereas at 25 degrees C, the reaction times ranged from 60 to 100 min. Therefore, this ultrafast synthetic method provided access to PMMA-b-PVC-b-PMMA, regardless of the reaction temperature, in the same range of reaction times as the induction period of the same reactions carried out at 90 degrees C in diphenyl ether and catalyzed by CuCl/2,2'-bipyridine. (c) 2005 Wiley Periodicals, Inc.