Commercial poly(vinyl chloride) (PVC) contains allyl chloride and tertiary chloride groups as structural defects. This article reports the use of the active chloride groups from the structural defects of PVC as initiators for the metal-catalyzed living radical graft copolymerization of PVC. The following monomers were investigated in graft copolymerization experiments: methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, butyl acrylate, methacrylonitrile, acrylonitrile, styrene, 4-chloro-styrene, 4-methyl-styrene, and isobornylmethacrylate. Cu(0)/bpy, CuCl/bpy, CuBr/bpy, Cu2O/bpy, Cu2S/bpy, and Cu2Se/bpy (where bpy = 2,2'-bipyridine) were used as catalysts. Living radical polymerizations initiated from 1-chloro-3-methyl-2-butene, allyl bromide, and 1,4-dichloro-2-butene as models for the allyl chloride structural defects: and from 3-chloro-3-methyl-pentane and 1,3-dichloro-3-methylbutane as models for the tertiary chloride defects were studied. Graft copolymerization experiments were accessible in solution, in a swollen state, and in bulk. (C) 2001 John Wiley & Sons, Inc.