From the self-assembly of the typical Salen-type Schiff-base ligand H2L and Zn(OAc)2·2H2O in the molar ratio of 1:1 or 1:2, the mononuclear [Zn(L)(H2O)](1) or binuclear [Zn2(L)(OAc)2(H2O)](2) are obtained, respectively. For both complexes 1 and 2, the unsaturated five-coordinate coordination environment to the catalytic active centers(Zn2+ ions) permits the monomer insertion for the effective solution copolymerization of cyclohexene oxide and maleic anhydride. All the solution copolymerizations afford poly(ester-co-ether)s, while lower catalyst and co-catalyst concentrations are helpful for the formation of alternating polyester. Of the three co-catalysts, 4-(dimethylamino)pyridine is found to be the most efficient, while an excess thereof is detrimental for chain growth of the copolymers. From the self-assembly of the typical Salen-type Schiff-base ligand H2L and Zn (OAc) 2-2H2O in the molar ratio of 1: 1 or 1: 2, the mononuclear [Zn (L) For two complexes 1 and 2, the unsaturated five-coordinate coordination environment to the catalytic active centers (Zn2 + ions) permits the monomer All the solution copolymerizations afford poly (ester-co-ether) s, while lower catalyst and co-catalyst concentrations are helpful for the formation of alternating polyester. Of the three co- catalysts, 4- (dimethylamino) pyridine is found to be the most efficient, while an excess thereof is detrimental for chain growth of the copolymers.