The focus of this paper is to study the liquid-liquid extraction process for the separation of toluene from alkane employing the ionic liquids N-butylpyridinium nitrate, [BPy][NO3], and N-hexylpyridinium nitrate, [HPy][NO3], as a new solvents. New experimental data for the ternary systems of {[BPy][NO3] (1) + heptane, or octane, or decane (2) + toluene (3)} and {[HPy][NO3] (1) + heptane, or octane, or decane (2) + toluene (3)} at T = 298.15 K and atmospheric pressure are reported. The Othmer-Tobias and Hand correlation are examined to check the reliability of the experimental LLE data. The toluene distribution ratios and selectivity were calculated form the experimental data. The selectivity values are higher than unity which indicates the ILs, [BPy][NO3] and [HPy][NO3], used in this work are potential solvents to separate toluene from alkane. Besides, the effect of the alkane chain length in the selectivity values was evaluated. In addition, the result of the NRTL thermodynamic modeling shows, the experimental data were satisfactorily correlated. (C) 2016 Elsevier Ltd.