Isobaric vapor-liquid equilibria for the binary system chloroform + methanol as well as the vapor-liquid equilibria for the chloroform + methanol + [emim][triflate] ternary system have been obtained at 100 kPa using a recirculating still. The ternary ionic liquid (IL) system presents in immiscibility zone at high chloroform composition, which increases with the temperature. Liquid-liquid equilibria for this system have also been determined. The measured ternary vapor-liquid equilibrium data were correlated using the Mock's electrolyte nonrandom two-liquid (NRTL) model which reproduces reasonably well the experimental values and predicts the total disappearance of the azeotrope when the mole fraction of ionic liquid in the liquid phase is 0.25. The immiscibility does not affect file use of [emim][triflate] its the entrainer for the complete chloroform + methanol separation.