Isobaric vapor-liquid equilibria for the binary systems chloroform + ethanol and chloroform + 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][triflate]) as well as the vapor-liquid equilibria for the chloroform + ethanol + [emiml [triflate] ternary system have been obtained at 100 kPa using a recirculating still. Both binary and ternary systems containing ionic liquid present an immiscibility zone at high chloroform composition, which increases with temperature. Also, liquid-liquid equilibria for both systems have been determined. The measured ternary VLE data were correlated using Mock's electrolyte NRTL model which reproduces reasonably well the experimental values. The detected immiscibility does not affect the use of [emim][triflate] as an entrainer for the complete chloroform + ethanol separation, and the azeotrope has totally disappeared when the mole fraction of ionic liquid in the liquid phase is 0.21.