In this work, three entrainers were selected to separate the azeotrope of dimethyl carbonate (DMC) and methanol, which were dimethyl sulfoxide, anisole, and diethyl oxalate. The vapor-liquid equilibrium (VLE) data of four binary systems (DMC + dimethyl sulfoxide, DMC + anisole, DMC + diethyl oxalate, and methanol + diethyl oxalate) were measured using a modified Rose-type circulating still at 101.3 kPa. The Van Ness point-to-point test and infinite dilution test were used to test the thermodynamic consistency of the experimental VLE data. The nonrandom two-liquid, universal quasi-chemical, and Wilson models were used to correlate the measured VLE data. The binary interaction parameters of the three models were regressed.