In this paper, liquid-liquid equilibrium (LLE) data for a ternary system of water + methanol (MeOH)+ methyl acetate (MA) at 303.15 K and a quaternary system of water (1)+ Me0H (2)+ MA (3) + potassium acetate (KOAc) at 283.15 K and 303.15 K have been measured at atmospheric pressure. Liquid-phase splitting of the ternary system water + Me0H + MA can be enhanced by adding KOAc salt. Distribution coefficients and separation factors corresponding to different concentrations of KOAc are obtained and the salt-out effects of calcium chloride and KAc have been compared. A modified non-random two-liquid (NRTL) model was used to correlate the experimental data, which considers the salt-effect on LLE. The model shows good performance for this correlation. (C) 2013 Elsevier B.V. All rights reserved.