Isobaric vapor–liquid equilibrium (VLE) data for the binary system of (methylcyclopentane + methylcyclohexane) and the ternary system of (methylcyclopentane + cyclohexane + methylcyclohexane) were measured at 101.3 kPa with a dynamic recirculating apparatue, and the temperature ranged from 344.79 to 373.85 K, and the thermodynamic consistency of the experimental date was checked by the Herington area method and Van Ness method. The experimental date was correlated with NRTL, Wilson and UNIQUAC activity coefficient models. The binary VLE date predicted by the binary interaction parameters agreed well with the experimental andliterature data. Then, Aspen plus V11 software was used to establish batch distillation model simulation calculation. The experimental results show that the products separated by the batch distillation model meet the requirements. Finally, two sets of 1300 kg/hr separation process were designed and the process was optimized. The energy consumption of scheme I was slightly less than scheme II.