We examined the feasible separation of ZrCl4 and HfCl4 through high pressure distillation as environmentally benign separation for structural material of nuclear power reactor. The bubble point pressures of ZrCl4 and HfCl4 mixtures were determined experimentally by using an invariable volume equilibrium cell at high pressure and temperature condition range of 2.3-5.6MPa and 440-490 ℃. The experimental bubble point pressure data were correlated with Peng-Robinson equation of state with a good agreement. Based on the vapor-liquid equilibrium properties evaluated from the experimental data, the feasibility of high pressure distillation process for the separation of ZrCl4 and HfCl4 was investigated with its main design condition through rigorous simulation using a commercial process simulator, ASPEN Hysys. An enhanced distillation configuration was also proposed to improve energy efficiency in the distillation process. The result showed that a heat-pump assisted distillation with a partial bottom flash could be a promising option for commercial separation of ZrCl4 and HfCl4 by taking into account of both energy and environmental advantages.