Na(2)S(2)O4-catalyzed single-electron transfer - degenerative chain transfer-mediated living radical polymerization (SET-DTLRP) of VC initiated with the bifunctional initiators 1,2-bis(iodopropionyloxy)ethane, dimethyl 2,5-diiodohexanedioate, and bis(2-methoxyethyl)-2,5-diiodohexanedioate as well as the tetrafunctional initiator pentaerythritol tetrakis(2-iodopropionate) is reported. This SET-DTLRP was performed in water at ambient temperature in the presence of polyvinyl alcohol and hydroxypropyl methylcellulose surfactants and provides methods for the synthesis of alpha,omega-di(iodo)PVC with two identical active chain ends and of four-arm star PVC with four identical active chain ends. These difunctional and tetrafunctional derivatives of PVC are also macroinitiators for the synthesis of ABA triblock copolymers and four-arm star block copolymers. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 635-652, 2009