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The vapor pressures of ZrCl4 and HfCl4 over a molten salt mixture of KC1 + AICI3 (1:1.04 mol) + XC14 (X = Zr, Hf) was determined in the temperature range of 485-627 K by the transpiration technique. The compositions of ZrCl4 and HfCl4 in the molten salt system were chosen such that it would be useful for vapor phase separation of ZrCl4 from Zr(Hf)Cl4 by an extractive distillation technique employing KC1 + AICI3 as the fused salt solvent. The relative volatility factor of pmcijpzrcu over the KC1 + AICI3 + XC14 (X = Zr, Hf) molten salt systems was determined to be 1.5 in the composition range of 16-30 mol % HfCl4 or ZrCl4. This indicated the possibility of separation of ZrCl4 and HfCl4 by extractive distillation with KC1 + AICI3 molten salt solvent at ambient pressure.