A novel constant total reflux batch distillation with top accumulation was proposed in this paper. Its characters lie in multimiddle vessels setting along the column, keeping constant total reflux during the whole operation, liquid transfer from one vessel to the one above, and liquid accumulated in the top vessel is withdrawn and collected to the product tank. Mathematical model was founded and the process was simulated by Matlab. Under the optimal distribution of middle vessels, compared with ordinary reflux ratio operation, the new operation could save time by about 50% when the target product concentration is the same. Finally, this operation mode was verified by separation experiment of acetic acid and water, and the column run stablely and was easy to control.