In this work, the feasibility of using 1-ethyl-3-methylimidazolium acetate ionic liquid, [EMim][OAc], as a solvent for the extraction of toluene from a mixture of heptane and cyclohexane was analyzed. Liquid-liquid equilibrium (LLE) data for the {heptane (1) + cyclohexane (2) + toluene (3) + [EMim][OAc] (4)} quaternary system and for the corresponding ternary systems were measured at 298.15 K and atmospheric pressure. Selectivities and solute distribution ratios were calculated from the experimental LLE data, and the obtained values were compared with those obtained for the {heptane or cyclohexane (1) + toluene (2) + [EMim][OAc] (3)} ternary systems. Finally, the experimental results for the ternary and quaternary systems were correlated with the nonrandom two-liquid thermodynamic model.