The invention discloses a metal cyanide coordination catalyst and a preparation method and application thereof. The catalyst has the structural formula of M1a[M2(CN)bL1c]d(X)m(L2)n.xSu.yL3.zH2O. The method for preparing the metal cyanide coordination catalyst comprises the following steps of: regulating mixed solution I' which consists of L3, M3e[M2(CN)bL1c]f, deionized water I, alcohol and/or an ether solvent to have a pH value of less than 7; and adding the solution I' into mixed solution II' which consists of M1(X)g salt, Su or a Su precursor, and deionized water II, and stirring for reaction at the temperature of between 20 and 120 DEG C for 0.5 to 200 hours; and separating, drying, the repeatedly dispersing to form slurry in an anhydrous organic solvent in which L2 is dissolved, distilling, separating and drying to prepare the metal cyanide coordination catalyst. The catalyst has the advantages of porous structure of less than 100nm, presence of coordination of M1 and L2 on a chemical structure, and obvious alternative selectivity in the process of catalyzing the copolymerization of epoxide and carbon dioxide.