Liquid-liquid equilibria (LLE) of water + acetic acid + dimethyl carbonate were experimentally specified at (298.2, 308.2, and 318.2) K. Each diagram was obtained through specifying binodal curves and tie-lines. The reliability of the experimental tie-line data was calculated by the OthmerTobias correlation. The nonrandom two-liquid (NRTL) and unified quasichemical activity coefficient (UNIQUAC) models were used to obtain the binary interaction parameters of the experimental tie-line data. However, universal functional (UNIFAC) and modified UNIFAC methods were used as well to predict the phase equilibrium in the system specified from experimental data using the interaction parameters between CH3, OCOO, COOH, and H2O functional groups. Distribution coefficients and separation factors were assessed for the immiscibility region.