A study was performed for amylose tris(3,5-dimethylphenylcarbamate) or, ADMPC, chiral stationary phase (CSP), to obtain information on how chiral discrimination occurs using chromatography, NMR and computational methods.Chromatographic study reveals that the mobile phase achiral additive played an important role in the enantioselectivity for polysaccharide-based stationary phases.The acidic additive ethanesulfonic acid had an enormous impact on the chiral selectivity of amino acid esters.The improved chiral selectivity was largely due to the longer retention of the later eluting enantiomer.The retention behavior of amines indicated that the higher selectivity for amino acid esters was due to increased hydrogen bonding donation by the amine group of the analyte.