Methanol and acetonitrile form a minimum azeotrope at 336.74 K, which contains methanol 76.89 mas%. The simulation and the experiment to separate the mixture by batch extractive distillation using aniline as entrainer is performed. Based on the experimental and simulative VLE data, aniline is chosen to be the suitable solvent. The sensitivity analysis about the number of stages, the refl ux ratio, the solvent feed stage and the solvent fl ow rate is conducted to obtain the optimal parameters and confi guration of the extractive distillation column with minimal energy requirements. The most appropriate confi guration is 30 theoretical stages. The optimal entrainer feeding stage is 8 with a solvent fl ow rate of 20kg/h and the refl ux ratio of 2.0, respectively. The simulation results show the effect of the main variables on the extractive distillation process. The experiment is carried out to corroborate the feasibility of the separation of methanol-acetonitrile by batch extractive distillation.