Glycerol dimethyl ether (2,3-dimethoxy-1-propanol) is one kind of potential fuel additive that can be synthesized from methanol and epichlorohydrin with high selectivity. The isobaric vaporliquid equilibrium data (VLE) for two binary systems, methanol (1) + epichlorohydrin (2) and methanol (1) + glycerol dimethyl ether (3) were measured in a modified Ellis recirculation still at 101.3 kPa. The VLE data were correlated using the nonrandom two-liquid (NRTL) and universal quasichemical activity coefficient (UNIQUAC) models, The calculated compositions and temperature by NRTL agree better with the experimental values than those calculated by UNIQUAC. The obtained model parameters of the binary systems are used to predict the VLE data for the ternary system.