In this work, two ionic liquids 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, [EMpy][NTf2], and 1-methyl-3-propylpyridinium bis(trifluoromethylsulfonyl) imide, [PMpy][NTf2], were investigated as possible solvents in the extraction processes for the ethanol removal from its mixtures with heptane and hexane. Hence, the experimental determination of the (liquid + liquid) equilibrium (LLE) for the ternary systems {heptane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {hexane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {heptane (1) + ethanol (2) + [PMpy][NTf2] (3)} and {hexane (1) + ethanol (2) + [PMpy][NTf2] (3)} at T = 298.15 K and atmospheric pressure was carried out. The solute distribution ratio and selectivity were calculated to evaluate the capability of these ionic liquids for the extraction of ethanol. Moreover, comparisons with other ILs taken from the literature were made. Finally, the experimental LLE values were compared with the correlated values obtained by means of the NRTL thermodynamic model. (C) 2013 Elsevier Ltd. All rights reserved.