Rare-earth ternary catalysts Y(CC13COO)3-ZnR2-glycerin were prepared for the copolymerization of carbon dioxide and propylene oxide (PO), where dialkylzincs (ZnR2) were diethylzinc, di(n-propyl)zinc, ali(n-butyl)zinc, di(i-propyl)zinc, di(i-butyl)zinc, di(s-butyl)zinc,respectively. The Y(CCl3COO)3-ZnR2-glycerin catalysts displayed the highest catalytic activity at the molar ratio of Y(CCl3COO)3:ZnR2:glycerin = 1:20:10. In the same copolymerization condition,catalysts containing dialkylzincs with branched alkyl group showed lower catalytic activity than that with primary alkyl group. For those catalysts including dialkylzincs with primary alkyl group, their catalytic activity decreases with increasing number of carbon atom in the alkyl group with the following sequence: Y(CCl3COO)3-ZnEt2-glycerin > Y(CCl3COO)3-Zn(n-Pr)2-glycerin>Y(CCl3COO)3-Zn(n-Bu)2-glycerin. However, the alkyl group in the dialkylzinc does not influence the insertion of PO into the propagation chain end.