Isobaric vapour-liquid equilibria (VLE) have been experimentally determined for the binary systems hexane + dimethyl carbonate (DMC), DMC + heptane, DMC + octane and cyclohexane + DMC at 101.3 kPa. The activity coefficients were found to be thermodynamically consistent and were satisfactorily correlated with the Wilson and UNIQUAC equations. Interaction parameters related to the carbonate group (-OCOO-) and alkanes and cy-cloalkanes, in ASOG and UNIFAC models, have been determined using our VLE data. The experimental results, as well as those by other authors, agree with the calculated VLE using the new ASOG and UNIFAC parameters.