Herein the first reported preparation of diblock copolymers of the polyethylene-like polyester poly(-pentadecalactone) (PPDL) via a combination of enzymatic ring-opening polymerization (eROP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization techniques is described. PPDL was synthesized via eROP using Novozyme 435 as a catalyst and a bifunctional initiator/chain transfer agent (CTA) appropriate for the eROP of -pentadecalactone (PDL) and RAFT polymerization of acrylic and styrenic monomers. Chain growth of the PPDL macro-CTA was performed to prepare acrylic and styrenic diblock copolymers of PPDL, and demonstrates a facile, metal-free, and greener alternative to preparing acrylic diblock copolymers of polyethylene (PE). Diblock copolymer architecture was substantiated via analysis of H-1 NMR spectroscopic, UV-GPC chromatographic, DSC onset crystallization (T-c), and MALDI-ToF mass spectrometric data. (c) 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3326-3335