The separation of p-cresol/2,6-xylenol mixtures has been investigated by extractive distillation in the presence of alkanolamines. The interaction parameters of liquid phase models, such as Wilson, NRTL, and UNIQUAC, have been estimated from binary vapor-liquid equilibrium data. The predicted relative volatility values for the p-cresol/2,6-xylenol mixtures in the presence of the alkanolamines were compared with experimental data.