During recent last years, outstanding properties of ionic liquids such as low melting point, large liquid range and negligible volatility have turned them into possible volatile organic solvents replacers to break alcohol-alkane azeotropic mixtures. On this basis, two ionic liquids, butyltrimethylammoniumbis(trifluoromethylsulfonyl) imide, [BTMA][NTf2], and tributylmethylammoniumbis(trifluoromethylsulfonyl) imide, [TBMA][NTf2], were studied through ternary liquid+ liquid equilibrium (LLE) of {alkane(1) + alcohol (2) + IL(3)} at T = 298.15 K and atmospheric pressure in order to consider the effect of ionic liquid cation alkyl chain length on the extraction process. The ILs capability as azeotrope breakers was determined by the calculation of parameters such as solute distribution ratio, b, and selectivity, S and this capability was compared with other bis (trifluoromethylsulfonyl) imide based ionic liquids from literature. The consistency of tie-line data was ascertained by applying the Othmer-Tobias and Hand equations. Finally, the experimental LLE were correlated by the Non Random Two Liquid (NRTL) thermodynamic model. (C) 2013 Elsevier Ltd. All rights reserved.