Herein, we explored the isobaric vapor-liquid equilibrium (VLE) data of ethyl acetate + acetonitrile and ethyl acetate + acetonitrile+1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM] [NTf2]). The VLE data were obtained in a CE-2 still (at 101.3 kPa). [BMIM] [NTf2] effected a evident "salting-out effect", altering relative volatility (alpha(12)), activity coefficient (gamma(i)), and minimum boiling point. The e-NRTL model, which was short for electrolyte-NRTL, was used to correlate with the experimental results. Furthermore, the parameters (a(ij), Delta g(ij), Delta g(ji)) were obtained and there was a good consistency between experimental and correlated results. The needed amount of [BMIM] [NTf2] was 0.027 as calculated by e-NRTL model to eliminate the azeotropy.