Isobaric vapor-liquid equilibrium data at 95.96 kPa for the three binary systems of dimethoxymethane with hexane, cyclohexane, and benzene are determined. A Swietoslawski-type ebulliometer is used for the measurements. The experimental T-x data are used to estimate Wilson parameters, and these parameters in turn are used to calculate vapor-phase compositions and activity coefficients. The activity coefficients are useful to calculate excess Gibbs function (G(E)/RT). All the systems studied here do not exhibit azeotropes. Excess Gibbs function values are positive over the entire range of composition for all the systems. Excess enthalpies are reported for the binary systems of dimethoxymethane with hexane, cyclohexane, and benzene at 298.15 K. The H-E data are interpreted on the basis of intermolecular interactions between unlike molecules.