Although carbon dioxide (CO2) is well known as one of the major green-house gases, it is also an economical C1 resource. Thus, CO2has been regarded as an appealing starting material for the synthesis of polymers, like polycarbonates by the reaction with epoxides. Herein the reaction between natural epoxidized soybean oil (ESO), propylene oxide (PO) and CO2under high pressure (4.0MPa) with the presence of Co-Zn double metal cyanide (Co-Zn DMC) catalyst was studied. Temperature and reaction time were varied accordingly and the products obtained were characterized by FTIR, GPC and1H NMR. The results obtained indicate the formation of polycarbonates in the samples collected with yields vary from 60 to 85%. The number average molecular weight (Mn) of the resultant polymer prepared at reaction temperature of 80°C and reaction time of 6h can reach up to 6498g/mol.