In this work, experimental liquid-liquid equilibria data of the systems 4-methyl-2-pentanone + ethanol + water and 4-methyl-2-pentanone + n-butanol + water are presented. The liquid-liquid equilibria of both systems have been measured between 283.2 and 323.2 K. The NRTL and UNIQUAC models were applied to fit the data for both ternary systems. The interaction parameters obtained from both models successfully correlated the equilibrium compositions. The binodal lines were compared to the values predicted by the UNIFAC-LLE and UNIFAC models. Moreover, the solvent capability of 4-methyl-2-pentanone was checked in order to separate these azeotropic mixtures alcohol + water. (C) 2012 Elsevier B.V. All rights reserved.