Abstract: The dissociation and motion state of Na₂WO₄ and CaWO₄ in the molten were analyzed qualitatively based on the characterization of molten salt electrolytic process and tungsten powder products in NaCl-KCl-Na₂WO₄ and NaCl -KCl -CaWO₄ system. The results show that there was a big difference between the electrolytic dissociation and ion movement forms of Na₂WO₄ and CaWO₄ in the electrolysis process due to different structures of active material, external conditions, electrolyte system, electron transfer and diffusion process. Concentration polarization of electrode is still the domination step in the electrolysis process.