We report here an efficient one-port synthesis of terpolymers from PO, CO2, and l-lactide (LLA) with long LLA rich sequence using the cheapest zinc adipate as catalyst. The copolymerizations were carried out under various experimental conditions to find out the optimal conditions. The terpolymer yields increase significantly from 151 to 417 (g polymer per g zinc) by the introduction of LLA as a third monomer. The polycarbonate moiety selectivity increases by nearly 60% at relatively high polymerization temperature (80 degrees C). Moreover, the differences in reaction kinetic of polycarbonate and polyester moieties were observed by in situ infrared monitoring. As confirmed by XRD and DSC, the synthesized terpolymers are a kind of semicrystalline polymer in which the crystalline PLA segment function as strong noncovalent crosslinking domains. Consequently, it exhibits much better thermal properties as well as remarkable higher mechanical strength compared with amorphous polycarbonate PPC. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1734-1741