Aliphatic polycarbonate (PC) copolymer is synthesized by ring opening copolymerization of acrylate- and allyl-functional cyclic carbonate monomers. The post-polymerization functionalization of the resulting copolymer is performed quantitatively using a variety of thiol compounds via sequential Michael addition and photo-induced radical thiol-ene click reactions within relatively short reaction time at ambient temperature. This metal-free click chemistry methodology affords the synthesis of biocompatible PC copolymer with multifunctional groups. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1581-1587