Isothermal vapor-liquid equilibrium (VLE) data for five binary systems ethyl acetate +3-methyl-1-butanol, ethanol +3-methyl-1-butanol, ethyl acetate+2-methyl-1-butanol, ethanol +2-methyl-1-butanol, ethyl acetate+2-methyl-1-propanol, involved in the alcoholic distillation have been determined experimentally by headspace gas chromatography. The composition in the liquid phase was corrected with the help of an iterative method by means of a G(E) model. However, due to the large density difference between the liquid and the vapor, the correction of the liquid phase composition is nearly negligible. All the binary mixtures show positive deviations from Raoult's law. The experimental VLE data are well predicted by using the modified UNIFAC model (Dortmund). (C) 2008 Elsevier B.V. All rights reserved.