In this paper, the liquid-liquid extraction of benzene from hexane with 1-propyl-3-methylimidazolium bis{trifluoromethylsulfonyl} imide, [C(3)mim][NTf2], as solvent was studied. The liquid-liquid equilibrium (LLE) data of the ternary system [hexane + benzene + ionic liquid] were measured at 298.15 K and atmospheric pressure. From the experimental composition data, the selectivity and the solute distribution ratio were calculated. The reliability of the experimental LLE data was ascertained using the Othmer-Tobias equation, and the NRTL thermodynamic model was used to correlate the experimental data. Moreover, a comparison with literature data for the ternary systems [hexane + benzene + ionic liquid] was also carried out.