In this study, modeling and optimization work were performed to obtain nearly pure anhydrous ethanol from aqueous ethanol mixtures using benzene as an entrainer. NRTL liquid activity coefficient model was adopted for phase equilibrium calculations and PRO/II with PROVISION 6.01, a commercial process simulator, was used to simulate the azeotropic distillation process. We used the total reboiler heat duties as an objective function and the concentration of ethanol at concentrator top as a manipulated variable. As a result, 76 mole percent of ethanol at concentrator top gave an optimum velue which minimized the total reboiler heat duties of three distillation columns.