This work comprises the separation of an azeotropic mixture (hexane/ethyl acetate) with two different ionic liquids, viz, (1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF4], and 1-ethyl-3-methylimidazolium dicyanamide, [EMIM] [DCA]. The liquid-liquid equilibrium (LLE) data for the two ternary systems were obtained at T = 298.15 K and at p = 101 kPa. Ionic liquids with the same cation but different anions (1-ethyl-3-methylimidazolium tetrafluoroborate or dicyanamide) were used to determine the ability to separate ethyl acetate from hexane. The efficiency to separate hexane + ethyl acetate with the investigated ionic liquids was assessed by calculating distribution ratios (beta) and selectivity (S) values for each system. These parameters revealed the influence of the effect of anions on the ionic liquids on LLE data. The ionic liquid containing dicyanamide [DCA] anions in comparison with tetrafluoroborate [BF4] revealed high selectivity and distribution ratio. The experimental tie lines were successfully correlated using the thermodynamic nonrandom two-liquid equation and were also used to compute the phase composition error in the mole fraction for the two ternary mixtures.