The single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate initiated with bromoform (CHBr3) and iodoform (CHI3) and catalyzed by Cu(0)/Me-6-TREN in DMSO at 25 degrees C provides a reliable method to prepare poly (methyl acrylate) (PMA) with active chain ends and controlled structure that can undergo subsequent functionalization to provide strategies for the synthesis of different block copolymers and other complex architectures. A detailed kinetic and structural analysis was used to assess the scope and the limitations of CHBr3 and CHI3 as initiators under SET-LRP conditions. (C) 2007 Wiley Periodicals, Inc.