A novel manganese(III) complex having an optically active N,N'-ethylenebis-beta-ketoimine ligand was prepared and characterized crystallographically. The manganese(III) complexes behave as effective catalysts in enantioselective epoxidation of unfunctionalized olefins by combined use of molecular oxygen, an oxidant, and pivalaldehyde, a reductant. Dihydronaphthalene derivatives were converted into the corresponding optically active epoxides with good to high enantioselectivities.