This research is focused on a study of the ionic liquid as a solvent in liquid-liquid extraction-of azeotropic mixtures. Liquid-liquid equilibria (LLE) were determined for the ternary systems ethanol + 2-butanone + 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), 2-propanol + 2-butanone + [BMIM][PF6], and 2-butanone + 2-propanol + 1,3-dimethylimidazolium methyl sulfate ([MMIM][MeSO4]) at 298.15 K and atmospheric pressure. Selectivity and distribution ratio values, derived from the tie lines data, were calculated. Experimental LLE data were correlated by means of the nonrandom two-liquid, Othmer-Tobias, and Hand equations. The plait point compositions have been calculated by the Hand method.