Dinuclear Co-salcy complexes bearing a dibenzofuran linker were explored for the copolymerizations of epoxides with cyclic anhydrides (CAs) or carbon dioxide [salcy = trans-N, N'-bis(salicylidene)-1,2-cyclohexanediamine]. It was found that the absolute configuration of the two Co-salcy moieties and the substituents on the salcy ligand greatly affect their catalyst activity. The optimized heterochiral dinuclear Co-salcy complex demonstrated one of the highest catalyst activities among the previously reported metal catalysts for the epoxide/CA copolymerization.