Liquid-phase composition values for {water + methanol + ethyl methyl carbonate (EMC)} and (water + ethanol + EMC) were determined at temperatures of 293.15, 303.15, and 308.15 K at 101 kPa. Thermodynamic modified UNIQUAC and extended UNIQUAC models were used in regression of the experimental values, with average root mean -square deviations of 0.96 and 1.45% in mole fraction, respectively. Moreover, optimum binary interaction parameters of (methanol or ethanol + EMC) were obtained by regression analysis of the phase composition values. The experimental data consistency was further ascertained by applying the Bachman equation. Distribution coefficients and separation factors were used to assess the extraction performance of EMC in the separation of methanol and ethanol from water.