The chloroiodomethyl chain ends of poly(vinyl chloride) (PVC) obtained by the single-electron-transfer/degenerative-chain-transfer mediated living radical polymerization of vinyl chloride initiated with iodoform were quantitatively functionalized by the reaction with 2-allyloxyethanol (CH2=CHCH2OCH2CH2OH). This reaction was performed in dimethyl sulfoxide at 70 degreesC and was catalyzed by sodium dithionite/ sodium bicarbonate. The resulting product is the first example of telechelic PVC [alpha,omega-di(hydroxy)PVC]. A possible mechanism for this reaction was suggested. (C) 2005 Wiley Periodicals, Inc.