Isobaric vapor-liquid equilibria (VLE) for the ternary system acetone + methanol +1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]) as well as the two solvent + IL binary systems have been obtained at 100 kPa using a recirculating still. The addition of [emim][DCA] to the solvent mixture produced a salting-out effect greater than that produced by other ionic liquids, showing that this ionic liquid is, until now, the best IL tested as an entrainer for the extractive distillation of the acetone + methanol mixtures, causing the azeotrope to disappear for an ionic liquid mole fraction as low as 0.031, at 100 kPa. This behavior can be explained on the basis of the influence of the IL concentration on the activity coefficient of each solvent in the binary mixtures. The electrolyte nonrandom two-liquid (NRTL) model was used for fitting successfully the experimental data.