The asymmetric Henry reaction is an efficient method for the synthesis of enantioenriched nitro alcohols. We investigated the catalytic activity and enantioselectivity of derivatives of Co–salen [salen = N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamine] in this reaction. Tetrahydro-salen (salan) complexes displayed a reversed enantioselectivity compared to their Schiff-base counterparts. Oligomeric Co–salen catalysts showed a higher activity than their small molecule analogues, indicating a bimetallic pathway.