The boiling temperature at atmospheric pressure were measured for 12 binary systems within the range T = (316 to 379) K and seven ternary systems using a dual circulation (vapour + liquid) equilibrium still. The systems studied contained water, methanol, or ethanol with the following ionic liquids (ILs): manoethanolammonium acetate ([HMEA][Ac]), diethanolammonium acetate ([HDEA][Ac]), triethanolammonium acetate ([HTEA][Ac]), and diethanolammonium chloride ([HDEA][Ac]). The experimental VLE results of the IL-containing binary systems were correlated by NRTL equation, and the binary NRTL parameters were used for the prediction of VLE of ternary systems with average absolute deviation of 0.73 K in boiling temperature. The results indicate that [HDEA]Cl can be used as an efficient solvent for the extractive distillation of (ethanol + water) due to its notable salting-out effect, which lower the vapour pressure of water, increase the volatility of ethanol, and eliminate the azeotropic phenomenon of the (water + ethanol) at definite IL concentration. (C) 2008 Elsevier Ltd. All rights reserved.