2,2,2-trifluoroethanol (TFE) is used more and more widely in industry, but there are few reports on its separation at present. The purpose of this work is to explore the feasibility of separating 2,2,2-trifluoroethanol from aqueous solution using different extractants, as isopentanol, 2-Ethyl-1-hexanol, n-Propyl acetate, and dichloromethane. The liquid–liquid equilibrium data of TFE + water +{isopentanol or 2-ethyl-1-hexanol or n-propyl acetate or dichloromethane} at standard pressure and 303.2 K were measured. The estimated partition coefficient (D) and separation factor (S) of TFE are higher than 1. Meanwhile, Othmer-Tobias and Hand's empirical equations verified the experimental data's consistency, and the squares of its linear correlation are all greater than 0.99. The NRTL and UNIQUAC activity coefficient models were used to correlate the experimental data, and different model parameters were obtained by regression. After comparing the calculated values of the model with the experimental data, it was found that the root means square deviation (RMSD%) was less than 0.34%, which indicate that both models have a reasonable correlation with the experimental data of the ternary system and can accurately predict the experimental data.