In the present study, modelling and optimization of ethanol-benzene separation process were performed using pressure-swing distillation. Order to obtain a reliable results, vapour-liquid equilibrium (VLE) experiments of ethanol-benzene binary system were performed. The parameters of thermodynamic equation were determined using experimental data and the regression. The pressure-swing distillation process optimization was performed to obtain high purity ethanol and high purity benzene into a low-high pressure columns configuration and a high-low pressure columns configuration. The heat duty values of the reboiler from simulation were compared, and the process was optimized to minimize the heat duty.