The knowledge of liquid-liquid equilibria (LLE) of the ternary systems (alkane/toluene/ionic liquid) is essential to develop thermodynamic models for liquid-liquid extraction of aromatics such as toluene from its mixtures with aliphatic hydrocarbons. In this study, new experimental LLE data for the ternary systems (hexane and heptane/toluene/1-methyl-3-octylimidazolium tetraflouroborate) are measured at T = 298.15 K and atmospheric pressure. The capability of ionic liquid for extracting toluene from its azeotropic mixture with aliphatic hydrocarbons (hexane and heptane) has been evaluated by the selectivity and solute distribution coefficients. The Othmer-Tobias equation has been applied to check the consistency of the experimental tie-lines. Finally, the obtained experimental LLE data are satisfactorily correlated by the nonrandom two-liquid model.