The invention provides a double-metal cyanide catalyst for copolymerization of carbon dioxide and epoxide. The structural formula is M1a [M2 (CN) bLc] dXi, and the catalyst is obtained by mixing a complex M1LX of metal M1, cyanide of metal M2 and metal salt M1eXf and performing reaction under mechanical ball milling, wherein M1LX is a compound with a structure as shown in the following formula (II) which is described in the specification, M2 is selected from one of Co<2+>, Co<3+>, Fe<2+>, Fe<3+>, Cd<2+> and Mn<3+>, and X is selected from one or more of F<->, Cl<->, Br<->, I<->, NO3<->, SO4<2->or organic carboxylate anions. The preparation method of the catalyst is simple, convenient and green, the catalyst is high in catalytic efficiency, good in activity and good in stability, and in a carbon dioxide / epoxide copolymerization reaction, higher catalytic activity and higher selectivity of a polymer product and polycarbonate chain links on a polymer main chain can be embodied in a polymerization reaction under the conditions of relatively lower catalyst concentration and higher initiator concentration.