2,2'-Dihydroxybenzil is demonstrated to be a highly diastereoselective stereodynamic receptor for the chiral recognition of amino alcohols. The receptor by forming diimine compounds with amino alcohols showed good (11:1) to excellent (>50:1) diastereoselectivity in chloroform. The existence of intramolecular hydrogen bonding with amino alcohols only in an axial conformer is demonstrated by H NMR and CD spectroscopy, X-ray crystallography, and DFT computations. The exciton chirality method can be used with diazo-attached 2,2'-dihydroxybenzil.