Novel optically active rare earth complexes have made possible a catalytic asymmetric nitroaldol reaction for the first time. Structural elucidation reveals that the complexes consist of one rare earth metal, three lithium atoms, and three BINOL units. Applications of the catalytic asymmetric nitroaldol reaction to syntheses of several p-blockers and erythro-AYA have been also achieved. Although the lithium containing rare earth-BINOL complexes are not effective for Michael reactions, another lithium free lanthanum-BINOL complex prove to be quite effective in catalytic asymmetric Michad reactions to give adducts of up to 95% ee.