Low transition temperature mixtures (LTFMs) are evaluated as potential entrainers for extractive distillation for the first time. The selected LTTMs were lactic acid-choline chloride 2:1 (LC 2:1), malic acid-choline chloride 1:1 (MC 1:1), glycolic acid-choline chloride 3:1 (GC 3:1) and glycolic acid-choline chloride 1:1 (GC 1:1). Vapour-liquid equilibrium (VLE) data for the pseudo-binary mixtures of water-LTFM and ethanol-LTTM were measured and fitted with the NRLT model to calculate the interaction parameters. These parameters were used to predict the pseudo-ternary VLE data using the same model. The prediction was compared with new experimental data for the water-ethanol-LTTM system and the prediction was found to be adequate. It was found that the ethanol-water azeotrope can be broken by MC 1:1, GC 1:1 and GC 3:1 and it can be moved to the pure ethanol side with LC 2:1. (C) 2014 Elsevier B.V. All rights reserved.