The first example of living radical polymerization of vinyl chloride carried out in water at 25 degreesC is reported. This polymerization was initiated by iodoform and catalyzed by nascent Cu-0 produced by the disproportionation of Cu-I in the presence of strongly Cu-II binding ligands such as tris(2-aminoethyl)amine or polyethyleneimine. The resulting poly(vinyl chloride) was free of structural defects, had controlled molecular weight and narrow molecular weight distribution, contained two similar toCHC(II) active chain ends, and had a higher syndiotacticity (62%) than the one obtained by conventional free-radical polymerization at the same temperature (56%). This novel polymerization proceeds, most probably, by a combination of competitive pathways that involves activation by single electron transfer mediated by nascent Cu-0 and degenerative chain transfer. (C) 2003 Wiley Periodicals, Inc.