Separating a mixture having an azeotrope or low relative volatility with single distillation column is difficult. Separating water-acetic acid mixture and water-ethanol mixture with a distillation column consumes a lot of energy. Pervaporation membrane can be used to separate the mixture in the concentration region where separation is difficult with distillation. We simulated a distillation-membrane hybrid process where membrane is located on the head of the distillation column for efficient separation of water-acetic acid and water-ethanol mixture. Permeability data were obtained from experiments and literature. We formulated an optimization problem for the process with total annual cost (TAC) as an objective function and major design variables as optimization variables. Major optimization variable affecting TAC of the hybrid process was shown to be distillate concentration. We also suggested a simplified optimization procedure to get a close-to-optimal solution.