New chiral Co-salen complexes with one C3-tBu group in the structure have been synthesized and applied as a chiral catalyst. A dimeric chiral salen having aluminum group metal salts such as AlCl3 displayed very high catalytic reactivity and enantioselectivity for the asymmetric ring opening of epoxides to synthesize optically pure α-aryloxy alcohols via phenolic kinetic resolution. The salen complexes immobilized on the inorganic support were also used as effective catalysts in that reaction. The identity of metal salts in the new chiral salen complex has proved to be important in the enantioselective reactions.