A steady-state equilibrium-stage model based on MESH equations was proposed to simulate saline extractive distillation columns. The interaction parameters between each component of water-CaCl2 and ethanol-water were obtained from mean ionic activity coefficients and vapor-liquid equilibrium (VLE) experimental data. Additionally, the interaction coefficients for the ethanol-CaCl2 pair were fitted to experimental VLE data which were reported by Nishi for the ethanol-water-CaCl2 system. It should be noted that adjustable parameters between each pair were considered to be temperature dependent. The results confirmed that the proposed model could accurately predict the experimental vapor-liquid equilibrium data for ethanol-CaCl2-water systems. Finally, the validated model was coded using MATLAB software and was solved using the Wang-Henke method, including the VLE and enthalpy models.