Phenolic compounds could be separated through their formation of deep eutectic solvent (DES). This process was different from normal liquid liquid extraction and was more efficient and environmental. In this work, the thermodynamic process of this kind of separation was studied. Ternary liquid liquid equilibrium data were systematically measured at atmospheric pressure and temperatures from 303.15 to 313.15 K. The experimental data were regressed by NRTL and UNIQUAC models, and the validated results revealed that NRTL model were more consistent with experimental data. The above mentioned parameters could be used to predict ternary mixture interactions and then applied in subsequent design and optimization of the separation process of corresponding systems. This extraction process was further optimized using Aspen Plus with NRTL as thermodynamic model. The simulation results were in good agreement with the experimental outcomes.