The objective of this study is the selection of a suitable entrainer for the separation of the binary azeotropic mixture, namely methanol + dimethyl carbonate (DMC) by extractive distillation. In this study, 2-ethoxyethanol and 4-methyl-2-pentanone were considered as entrainer candidates for the separation of methanol and DMC. Isobaric vapor-liquid equilibria (VLE) were measured for the ternary mixtures methanol + DMC + 2-ethoxyethanol and methanol + DMC + 4-methyl-2-pentanone, and for their constituent binary mixtures, under reduced pressures 01 66.66 kPa and 93.32 kPa. Experimental VLE data for the constituent binary mixtures were represented by the Wilson and the NRTL model. The VLE predictions for two ternary mixtures were compared with the experimental VLE data on the basis of the Wilson or NRTL parameters obtained from the constituent binary VLE data. The modified UNIFAC (Dortmund) model was also used for the prediction of the binary and ternary mixtures. The solvent effects of the two entrainer candidates investigated are discussed using the predicted results for the ternary mixtures and both 2-ethoxyethanol and 4-methyl-2-pentanone were found to be suitable entrainers for the separation of methanol and DMC. When the selectivity of 2-ethoxyethanol and 4-methyl-2-pentanone are compared, it could be concluded from the separation factors that 4-methyl-2-pentanone shows a higher selectivity. (C) 2011 Elsevier B.V. All rights reserved.