Two solvents, ethylene glycol and glycerol, are proposed as possible entrainers for the extractive distillation of the binary azeotropic mixture formed by ethanol and water. In this way, consistent isobaric vapour-liquid equilibrium data at 101.3 kPa were measured for the ternary systems ethanol+water+ethylene glycol and ethanol+water+glycerol. The data were correlated by local compositions models Wilson, NRTL and UNIQUAC. Parameters of these models were later employed to evaluate ability of the candidates to break the original azeotrope. The obtained results led to consider the ethylene glycol and the glycerol as valid entrainers for the extractive distillation process of ethanol and water. (C) 2013 Elsevier B.V. All rights reserved.