The coordination system, Y(CF3CO2)(3) (I)-Zn(Et)(2) (II)-m-hydroxybenzoic acid (III), was found to be the most active catalyst to generate poly(propylene carbonate) (PPC) from carbon dioxide and propylene oxide (PO) in 1,3-dioxolane. A high yield and a high molecular weight could be obtained at the conditions of a II/I molar ratio of 20, a II//II molar ratio of 1.0, a temperature of 60degreesC, and a pressure of 2.76 MPa. The carbonate content in the resultant PPC was found to be nearly 100%. The block copolymerization in the based PPC was carried out by in situ introducing an epoxide other than PO right after the copolymerization of carbon dioxide with PO using the same catalyst system. The IR and H-1 NMR spectra as well as the measured molecular weights verified the resulting copolymers were block copolymers. For the block copolymerization of CO2 with cyclohexene oxide and CO2 with 4-vinyl-1-cyclohexene-1,2-epoxide in the based PPC, the yield as well as the cyclohexene carbonate and the 4-vinyl-1-cyclohexene carbonate contents were found to increase with increasing temperature. The most appropriate temperature was around at 80degreesC. The weight-average molecular weights of the block copolymers lay in a range from 2.44 x 10(5) to 3.16 x 10(5), the polydispersity in a range from 5.0 to 6.3, and the 10% weight loss temperature in a range from 226 to 253degreesC. The thermal and mechanical properties of the resultant block copolymers lay between those of PPC, poly(cyclohexene carbonate), and poly(4-vinyl-1-cyclohexene carbonate), indicating the desired properties of a polymer can be achieved via block copolymerization.