Vapor-liquid equilibria of binary mixtures containing the high boiling solutes (dimethyl adipate, ethyl benzoate, and benzylamine) with the ionic liquid 1-methyl-3-ethylimidazolium bis(trifluoromethylsulfonyl) imide [EMIM][NTf2] were studied using the transpiration method. VLE measurements were carried out over the whole concentration range at temperatures between 298 K and 318 K. Activity coefficients (gamma(i)) of these solvents in the ionic liquid were determined from these data and are correlated by the NRTL equation. In addition, vapor pressures of the pure solutes dimethyl adipate and ethyl benzoate have been measured as a function of temperature, and their enthalpies of vaporization have been derived.