Using competitive frontal analysis, the binary adsorption isotherms of the enantiomers of 1-phenyl-1-propanol were measured on a microbore column packed with a chiral stationary phase based on cellulose tribenzoate. These measurements were carried out using only the racemic mixture. The experimental data were fitted to four different isotherm models: Langmuir, BiLangmuir, Langmuir–Freundlich and Tóth. The BiLangmuir and the Langmuir–Freundlich models accounted best for the competitive adsorption data. An excellent agreement between the experimental and the calculated overloaded band profiles for various samples of racemic mixture was obtained when the equilibrium dispersive model of chromatography was used together with the BiLangmuir competitive isotherm. The isotherm parameters measured under competitive conditions were used to calculate the overloaded band profiles of large samples of the pure S- and R-enantiomers, too. A satisfactory agreement between the experimental and calculated band profiles was observed when using in the computation the corresponding single component BiLangmuir isotherm derived from the binary isotherm previously determined. Thus only data derived from the racemic mixture are required for computer optimization of the preparative chromatography separation of the enantiomers.