Isothermal vapor-liquid equilibrium (VLE) data were measured for ethyl benzoate + ethanol and water + ethanol + ethyl benzoate at temperatures from 333.15 to 373.15 K. At vapor-liquid-liquid equilibrium (VLLE), the saturated pressures were determined experimentally for ethyl benzoate + water from 313.15 to 373.15 K, and both the saturated pressures and the compositions in the three coexistence phases were also measured for water + ethanol + ethyl benzoate at 333.15 and 353.15 K. No azeotrope was formed in ethyl benzoate + ethanol. Under ideal gas-phase assumption, the NRTL and the UNIQUAC models with linearly temperature-dependent parameters represent well the saturated pressures of ethyl benzoate + water at VLLE. The model parameters determined from the phase equilibrium data of the constituent binaries were applied to predict the VLE and VLLE properties for water + ethanol + ethyl benzoate. The UNIQUAC model and the UNIFAC-LLE (liquid-liquid equilibrium) model predict the binodal curves to within reasonable accuracy for this ternary system. By adjustment of six parameters simultaneously, the UNIQUAC model correlated satisfactorily the mutual solubility data of water + ethanol + ethyl benzoate.