Abstract: In order to optimize the technological conditions of cerium preparation by electrolytic reduction of molten salt, the electrochemical behavior of CeCl₃ in NaCl-KCl molten salt and the electrodeposition process on Mo electrode were carried out. The results indicate that Ce³⁺ can be quickly electrolyzed at the cathode potential more than 1.9 V (vs. Ag/AgCl) using Mo rod (ø4 mm). Increasing the concentration of Ce³⁺ is beneficial to the electrolytic reaction. The optimal electrolytic voltage is determined to be 4.41 V using two-electrode system, and the cathode potential is 2.27 V (vs. Ag/AgCl). It is found that the voltage increases with the decrease of cathode area when the anode area is fixed, and the cathode area is changed. Under the experimental conditions, the voltage varies linearly with the electrode center distance. Compared with the change of electrode center distance, the effect of current change on voltage is more significant.