Isobaric vapor-liquid equilibrium (VILE) data for the ethanol (1) + water (2) system containing the ionic liquid (IL) 2-aminoethanol tetrafluoroborate ([MEA](+)[BF4](-)) (3) at atmospheric pressure (101.3 kPa) were measured with a modified Othmer still. The results showed that the azeotropic point can be broken at a specific IL mole fraction, indicating a significant salting-out effect following the order of x(3) = 0.15 > x(3) = 0.10 > x(3) = 0.05. The IL [MEA](+)[BF4](-) may be a promising entrainer for the separation of ethanol and water with extractive distillation because it exhibits the highest separation ability when compared with other entrainers previously reported. The commonly used nonrandom two-liquid (NRTL) model was used for correlating the measured ternary VLE data.