Recovery of bioethanol from the fermentation broth is classically achieved by distillation. The design and optimization of the distillation requires a reliable thermodynamic model that describes sufficiently the properties of the ethanol/water mixture, and, especially, the vapor-liquid equilibrium (VLE) near the azeotropic point. The purpose of this study is twofold: first, to provide new reliable low-pressure VLE data for the ethanol/water mixture with emphasis given near the azeotropic region, and second. to develop new temperature-dependent binary interaction parameters for three excess Gibbs energy models (UNIQUAC, Wilson and NRTL), by fitting simultaneously VLE data, azeotropic points and excess enthalpies for this mixture. (C) 2011 Elsevier B.V. All rights reserved.