The water-ethanol system was studied experimentally to find the liquid-liquid equilibrium (LLE) data at various temperature values by using five different entrainers: cyclohexane, n-pentane, DEE (diethyl ether), DIPE (diisopropyl ether), and ETBE (ethyl tert-butyl ether). Ternary LLE data for water-ethanol-entrainer system was determined based on an experimental procedure. Exact liquid activity coefficient parameters were found by experimental data and LLE data was predicted. For this purpose, two thermodynamic models, NRTL and UNIQUAC, were compared and contrasted with experimental data to probe into the better thermodynamic model for the azeotropic processes of ethanol system. The most promising entrainer was found through root mean square and average absolute deviations.