Modified UNIFAC (Dortmund) parameters for the interactions of the amino group at cycloaliphatic hydrocarbon with the hydroxyl group or the methanol group were determined by means of literature and our own experimental data. The vapor-liquid equilibria of the three binary systems cyclohexylamine + 2-butanol, cyclohexylamine + 2-methyl-2-butanol, and cyclohexylamine + 1-hexanol were measured isothermally with the dynamic method. The predictions of phase equilibrium data using the new parameter set for the amino group at cycloaliphatic hydrocarbon are compared to the predictions using the amino group at aliphatic hydrocarbon. The improvement of the description of experimental data is shown for binary and ternary systems.