Various organometallic compounds (diphenylzinc, dibenzylzinc, dicyclohexylzinc, bis( pentafluorophenyl) zinc, diethylzinc, di(n-butyl) zinc, triethylaluminum) were used to form Y(CCl3COO)(3)-organometallic compound-glycerol catalyst for the copolymerization of carbon dioxide and propylene oxide. It was found that Y(CCl3COO)(3)-diphenylzinc-glycerol catalyst showed the highest catalytic activity, at optimum conditions the yield could be as high as 478.8 ( g polymer/mol Zn h). The catalytic activity sequence of these catalysts decreased as follows: Y(CCl3COO)(3)-diphenylzinc-glycerol > Y(CCl3COO)(3)-diethylzinc-glycerol > Y(CCl3COO)(3)-di-(n-butyl) zinc-glycerol > Y(CCl3COO)(3)-dibenzylzinc-glycerol > Y(CCl3COO)(3)-dicyclohexylzincglycerol > Y(CCl3COO)(3)-bis(pentafluorophenyl)zinc-glycerol. H-1 NMR, C-13 NMR, TGA, DMA, tensile tests results indicated that microstructure and properties of the polymers varied with catalyst used. Copolymer from Y(CCl3COO)(3)-diphenylzinc-glycerol catalyst displayed the highest thermal properties and mechanical properties: the glass transition temperature (T-g) was 50.2 degrees C, the 5% weight loss temperature (T-5%) was 222 degrees C, the tensile strength was 34.7 MPa, the Young's modulus was 298 MPa. The difference between the properties of the polymers was explained relating to the different polycarbonate content in the polymers.