A novel double metal cyanide complex (DMC) based on Zn[Ni(CN)4] was prepared using K2[Ni(CN)4] and ZnCl2, and employed as catalyst for the copolymerization of carbon dioxide and propylene oxide (PO). The resulting copolymers were characterized by IR, 1HNMR. The results show that this catalyst exhibits catalytic efficiency at approximate 500 g copolymer per gram of Zn[Ni(CN)4] under proper conditions. The mole fraction of CO2 for copolymer can reach about 0.3. Propylene carbonate is also produced as by-product, but its content is as low as 4%-6% of overall products under suitable conditions.