Isobaric vapor-liquid equilibria (VLE) for the binary systems methyl acetate + methanol and methyl acetate + 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][triflate]) as well as the VLE for the methyl acetate + methanol + [emim][triflate] ternary system have been obtained at 100 kPa using a recirculating still. The experimental binary data sets were independently fitted with the electrolyte NRTL model, and the parameters of Mock's model were estimated for each binary system. These parameters, together with those early obtained for methanol + [emim][triflate], were used to predict the ternary VLE, which agreed reasonably with the experimental values. The results suggest that the addition of [emim][triflate] to the methyl acetate + methanol mixture produced an important salting-out effect, and the azeotrope disappears when the mole fraction of ionic liquid in the liquid phase is greater than 0.129.