This work aimed the evaluation of a saline extractive distillation for the ethanol production. A thermodynamic model was used to predict the influence of the salts in the liquid-vapor equilibrium of the system water-ethanol and inside the packed column. The experiments were done in a distillation unit, with an internal diameter of 5.9 cm and a packing section with 37 cm of height, packed with raschig rings with 0.73 cm of characteristic inner made of glass. All the bottom and top samples were analyzed by refractive index. Two synthetic charges with the same composition of ethanol that are produced in the refinery (0.02 and 0.25 mol.L-1) were distilled under atmospheric pressure. Sodium chloride, calcium chloride, potassium acetate, calcium nitrate and a mixture of sodium and potassium acetates were added to the synthetic charges and the results were compared to the experiments already done without the presence of the salts, revealing the ethanol enrichment in the top product of the distillation unit, for all the systems analyzed. Another charge from the refinery, known as load of wine without yeast, was evaluated and the results indicated the same behavior, enriching the ethanol with the application of the saline extractive distillation. (C) 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.