Trace amounts of labile chlorines present in poly(vinyl chloride) (PVC) were found to act as initiation sites for the preparation of graft copolymers of PVC by copper-mediated atom transfer radical polymerization (ATRP). High grafting yields were attained during the graft copolymerizations of n-butyl acrylate (161.8%) and 2-ethyl hexyl acrylate (51.2%) in 7.5 h. In both cases, the grafting proceeded with first-order kinetics with respect to the monomer concentrations, this being typical for ATRP. Gel permeation chromatography traces of the resulting products did not exhibit additional peaks attributable to the formation of free homopolymers. The presented procedure offers an efficient means of preparing self-plasticized PVC structures. (C) 2003 Wiley Periodicals, Inc.