alpha,omega-di(iodo) poly(isobornyl acrylate) macroiniators (alpha,omega-di(iodo)PIA) with number average molecular weight From (M) over bar (n.TriSEC) = 11,456 to (M) over bar (n.TriSEC) = 94,361 were synthesized by single electron transfer-degenerative chain transfer mediated living radical polymerization (SET-DTLRP) of isobornyl acrylate (IA) initiated with iodoform (CHI3) and catalyzed by sodium dithionite (Na2S2O4) in water at 35 degrees C. The Plots of number average molecular weight us conversion and In{[M](0)/[M]} us time are linear, indicating a controlled polymerization. alpha,omega-di(iodo) poly(isobornyl acrylate) have been used as a macroinitiator for the SET-DTLRP of vinyl chloride (VCM) leading to high T-g block copolymers PVC-b-P1A-b-PVC. The dynamic mechanical thermal analysis of the block copolymers suggests just one phase indicating that copolymer behaves as a single material. This technology provides the possibility of synthesizing materials based oil PVC with higher T-g in aqueous medium. (C) 2009 Wiley Periodicals, Inc J Polym Sci Part A Polym Chem 47: 7021-7031, 2009