The selective nature of organic catalysts has been exploited to synthesize copolymers of the functional monomer, alpha-bromo-gamma-butyrolactone (alpha Br gamma BL), with trimethylene carbonate (TMC), 2-allyloxymethyl-2ethyl- trimethylene carbonate (AOMEC) and epsilon-caprolactone (epsilon CL) with excellent control. The high control is attributed to high selectivity and reactivity at ambient reaction temperatures, which suppresses the degree of side reactions (e.g., transesterification) that inherently plague this class of co-monomers. In particular, good results were obtained using diphenyl phosphate (DPP) as a catalyst, resulting in copolymers with low dispersities (D-M) (i.e., approximately 1.08) and number average molecular weights (M-n) of approximately 20,000 g/mol. The high control opened the possibility to construct more complex polymeric structures, exemplified via the synthesis of a multifunctional triblock copolymer composed of AOMEC as the center block, flanked with a statistical copolymer consisting of 3CL and aBrgBL. The subsequent grafting of methyl acrylate (MA) via Cu(0)-mediated CRP on the copolymers resulted in graft copolymers with a final D-M of less than 1.2. (C) 2016 The Authors. Published by Elsevier Ltd.