In this paper, the evaluation of the ionic liquid 1-ethylpyridinium ethylsulfate, [Epy][ESO4], on the extraction of benzene from cyclic hydrocarbons was carried out. With the aim of studying the influence of the cyclic hydrocarbon structure on the liquid extraction, the liquid-liquid equilibria (LLE) data of the systems: {cyclohexane, or cyclooctane, or methylcyclohexane or cyclohexene (1) + benzene (2) + [Epy]EESO4] (3)} have been experimentally determined at T=298.15 K and atmospheric pressure. Selectivity and solute distribution ratio, derived from the tie-lines, were used to determine the ability of this ionic liquid as solvent for the separation of benzene from its mixtures with cyclic hydrocarbons. The degree of consistency of the tie-lines was tested using the Othmer-Tobias equation, and the experimental LLE data were correlated using the Non-Random Two-Liquid (NRTL) model. Furthermore, the literature comparison for the system {cyclohexane (1) + benzene (2) + ionic liquid or solvent (3)} has been performed. The quantum chemical based COnductor like Screening MOdel for Real Solvent (COSMO-RS) model was used as a predictive tool to describe the experimental LLE data for the ternary systems {cyclohexane, or cyclooctane, or methylcyclohexane, or cyclohexene (1) + benzene (2) + [Epy][ESO4] (3)} and the obtained results have been compared with the experimental data. (C) 2013 Elsevier B.V. All rights reserved.