This work aims to study the vapor-liquid equilibrium (VLE) of the higher alcohols present in the ethanol distillation process. The VLE data for binary and ternary systems composed by 2-propanol, 2-methyl-1-propanol, and 3-methyl-1-butanol were measured at pressures of 101.3 kPa and 74.7 kPa. An ebulliometer apparatus (Fisher) was used to VLE data measurements, and the compositions of vapor and liquid phases were determined by gas chromatography. The VLE data were tested for thermodynamic consistency using the tests of Van Ness modified by Fredenslund and the area test. Binary interaction parameters for the liquid phase activity coefficients were adjusted using the Wilson, nonrandom two-liquid (NRTL), or universal quasichemical (UNIQUAC) models, and the vapor phase fugacity coefficients were calculated using the virial equation with the Hayden and O'Connell approach.