The separation of the enantiomers of various esters of N-TFA-amino acids on capillary columns coated with N-TFA-L-valyl-L-valine cyclohexyl ester was investigated and the chromatographic behavior discussed. For analytical purposes the isopropyl esters represent the best choice since they combine reasonable retention times with good resolution factors. Because of the limitations imposed by the maximum permissible working temperature of the phase (110°), mixtures are best analyzed in two steps. Columns of 400–500 ft serve for the resolution of alanine, α-amino butyric acid, valine, norvaline, isoleucine, alloisoleucine, leucine, norleucine, serine, threonine, allothreonine and proline, whereas for methionine, phenylalanine, aspartic and glutamic acid columns of 100–200 ft are recommended.