• The LLE data for water + 2,2,2-trifluoroethanol + solvents were measured. • The partition coefficient and separation factor were calculated. • The reliability of LLE data and binary interaction parameters were verified by the GUI-MATLAB. • The NRTL and UNIQUAC models were applied to correlate the LLE data. • The binary interaction parameter values were obtained from the data correlation. The liquid–liquid equilibrium (LLE) data of water, 2,2,2-trifluoroethanol (TFE) and different solvents {1-hexanol, 1-pentanol, 1-octanol and 2-octyl alcohol} were measured at 303.2 K under 101.3 kPa. The distribution coefficient (D) and selectivity factor (S) were calculated, and the results showed that the four extractants had good separation effects. The experimental data were successfully correlated by the two thermodynamic models of NRTL and UNIQUAC. In addition, the binary interaction parameters were obtained. The root mean square deviation (RMSD) of the fitting results were all less than 0.6%. The GUI-MATLAB was used to verify the consistency of the binary interaction parameters calculated by the thermodynamic models. [ABSTRACT FROM AUTHOR]