A novel azeotropic distillation for sulfuric acid recovery, which uses organic solvents as entrainers, is proposed. This new distillation process may provide significant energy savings. Vapor-liquid equilibria (VLE) data were determined by the quasi-static ebulliometric method for the following systems at (30, 60, and 90) kPa: (1) sulfuric acid + water + ethanol; (2) sulfuric acid + water + butyl acetate; and (3) sulfuric acid + water + butyl acetate + ethanol. Through the use of the OLI software, a chemical model was established via regressing the experimental data to obtain the mixed solvent electrolyte (MSE) model parameters. The average absolute deviations of boiling points for all systems are only 1.34 K. The new model with newly obtained parameters was successfully applied to predict the VLE for the sulfuric acid + water + butyl acetate ternary system at constant pressure, providing important VLE information for the recovery of spent sulfuric acid by this new azeotropic distillation technology.