In this study, isobaric vapor-liquid equilibrium (VLE) data for ternary systems of chloroform + isopropanol + 1,3-dimethylimidazolium dimethylphosphate ([MMIM][DMP]) were measured with a modified Othmer still at 1013 kPa. VLE data were correlated with the non-random two liquid (NRTL) model and the fitted results showed that [MMIM][DMP] produced a crossover effect between salting-in and salting-out on chloroform, and the minimum [MMim][DMP] concentration needed to break the azeotrope of the chloroform + isopropanol system was 0.045 (mole fraction). In the separation of chloroform and isopropanol by extractive distillation, [MMIM][DMP] was found to be an effective candidate entrainer. (C) 2018 Elsevier B.V. All rights reserved.