α,ω-Di(iodo)poly(2-ethylhexyl acrylate)s [α,ω-di(iodo)P2EHAs] with number-average molecular weights of 13,700 and 20,400 were synthesized by the singleelectron-transfer/degenerative-chain-transfer mediated living radical polymerization (SET-DTLRP) of 2-ethylhexyl acrylate initiated with iodoform and catalyzed by sodium dithionite in water at 23 and 30 ° C. These α,ω-di(iodo)P2EHAs were used as macroinitiators for the SET-DTLRP of vinyl chloride, which was carried out under similar reaction conditions to synthesize ABA block copolymers containing poly(vinyl chloride) in the A blocks and poly(2-ethylhexyl acrylate) in the B block. Poly(vinyl chloride)-b-poly(2-ethylhexyl acrylate)-b-poly(vinyl chloride) was synthesized with 100% initiator efficiency. This synthetic method provides for the first time access to a diversity of block copolymers and other complex architectures based on combinations of thermoplastic poly(vinyl chloride)and elastomeric polyacrylates. © 2005 Wiley Periodicals, Inc.