In this work, the ionic liquid [EPy][EtSO(4)] was tested as a solvent for the separation of benzene from alkanes. The liquid-liquid equilibrium (LLE) data for the ternary mixtures of octane (1) or nonane (1) + benzene (2) + 1-ethylpyridinium ethylsulfate ([EPy][EtSO(4)]) (3) at T = (283.15 and 298.15) K and atmospheric pressure were experimentally determined. The cloud-point method was used to determine the solubility curve, and the tie-line compositions were obtained by density measurements. The effectiveness of the extraction of benzene from an alkane was evaluated by means of the calculation of the solute distribution ratio and selectivity values. The consistency of tie-line data was ascertained by applying the Othmer-Tobias and Hand equations. A correlation of the experimental tie lines was conducted through the use of the nonrandom two-liquid (NRTL) equation, which provides a good correlation of the experimental data. The results show that [EPy][EtSO(4)] can be used as an alternative solvent in liquid extraction processes for the removal of benzene from its mixtures with alkanes.