Liquid-liquid equilibrium (LLE) data of ternary mixtures containing n-hexane, benzene and acetonitrile were measured at T= (298.15, 308.15 and 318.15) K under atmospheric pressure, respectively. The reliability of the experimental data was checked by Othmer-Tobias. Bachman and Hand correlations. Both the NRTL and UNIQUAC models were used to correlate the LLE data and the binary interaction parameters were obtained valid for the range of temperature studied. The two models correlated the LLE data well, and the NRTL model gave slightly better predicted results than UNIQUAC. The measured data can be used to design and optimize the separation process of benzene + acetonitrile system by azeotropic distillation method with n-hexane as entrainer. (C) 2014 Elsevier B.V. All rights reserved.