High-performance liquid chromatographic methods were developed for the separation of the enantiomers of five new aminonaphthol analogs possessing two chiral centers. The direct separations were performed on chiral stationary phases containing either amylose-tris-3,5-dimethylphenyl carbamate (Kromasil AmyCoat column) or cellulose-tris-3,5-dimethylphenyl carbamate (Kromasil CelluCoat column) as chiral selector. The experimental data are utilized to discuss the effects of the mobile phase composition, the nature of the alcoholic modifier and the specific structural features of the analytes on the retention and separation. The elution sequence was determined in all cases; no general regularities could be established.