The performance of two tetrafluoroborate-based ionic liquids (ILs) as entrainers in the dehydration of water/ethanol azeotropic mixtures was evaluated. Isobaric vapor-liquid equilibrium (VLE) data were measured for the systems ethanol/water/1-butyl-3-methyl imidazolium tetrafluoroborate and ethanol/water /n-butylpyridinium tetrafluoroborate including the azeotropic region. VLE data for the ethanol/water, ethanol/IL, and water/IL binary mixtures were obtained at 100 kPa. The hydrolysis of the tetrafluoroborate anion was studied for both types of ILs by(19)F NMR analysis. The hydrolysis of the tetrafluoroborate anion does not have much effect on the ethanol/water VLE. The(19)F NMR analysis indicated that hydrolysis occurred at high mole fractions of water.