Liquid-liquid equilibrium (LLE) data for the ternary system of water + methanol (MeOH)+ methyl acetate (MA) and the quaternary system of water + MeOH + MA + calcium chloride (CaCl2) have been measured at 283.15K under atmospheric pressure. The liquid-phase splitting of water + MeOH + MA can be enhanced by the addition of CaCl2. Separation factors at different CaCl2 concentrations were calculated and compared. In addition, the experimental data were correlated with the improved Eisen-Joffe equation. (C) 2011 Elsevier B.V. All rights reserved.