Objectives. To calculate the molar enthalpy of vaporization of binary homogeneous mixtures based on isothermal and isobaric vapor– liquid equilibrium data, and to compare the results of calculation of molar enthalpy of vaporization by different methods with experimental data.Methods. Simulation of the vapor–liquid equilibrium of binary systems according to the Non-Random Two Liquid “local compositions” equation and thermodynamic calculations of molar vaporization enthalpies of binary mixtures at different conditions of vapor–liquid equilibrium were used.Results. Arrays of calculated data were obtained with regard to molar enthalpies of vaporization for 25 compositions of binary azeotropes (isothermal, isobaric conditions of phase equilibrium), and the full range of compositions of the benzene–ethanol system at atmospheric pressure.Conclusions. The accuracy of thermodynamic methods for calculating the vaporization enthalpy of binary azeotropic mixtures according to vapor–liquid equilibrium data is higher in 85% of cases for isothermal, and in 75% of cases for isobaric conditions. By taking into account the influence of temperature on the activity coefficients of components in the liquid phase, the values of excess molar enthalpy both for azeotrope compositions and for the full concentration range of the benzene–ethanol system under isobaric conditions of liquid– vapor phase equilibrium can be accurately reproduced.