Hydroxyl-functionalized poly(propylene carbonate) (PPC) was synthesized by a zinc glutarate catalyst mediated terpolymerization of carbon dioxide (CO2), propylene oxide (PO), and 2-[[(2-nitrophenyl)methoxy]methyl]oxirane (monomer A). PPC with varying monomer A contents (0-10.6 mol %) were obtained and could be transformed into hydroxyl-functionalized PPC by ultraviolet (UV) light irradiation without backbone degradation. The process of removing o-nitrobenzyl (ONB) protecting groups was monitored by UV-vis spectrometry to proceed within minutes. Thermal properties and contact angles of the functionalized PPCs were measured, showing the expected increase in hydrophilicity and glass transition temperature with increasing content of hydroxyl entities.