Vapour-liquid equilibrium (VLE) and boiling point data have been measured for binary mixtures of N,N-dimethylformamide with substituted benzenes, of different compositions, in a Swietoslawski-type ebulliometer. The mixtures include N,N-dimethylformamide with ethylbenzene; as well as chlorobenzene, and bromobenzene, with aniline. The measurements were made at 712 mm Hg. The experimental temperature-mole fraction data were used to estimate Wilson parameters, These, in turn, were used to calculate vapour compositions, boiling points and activity coefficients, from which the excess Gibbs free energies G(E) were calculated. The observed and calculated values are interpreted in terms of specific interaction.