It is necessary to understand electrochemical phenomena to optimize the operation conditions and design an electrolytic cell system suitable for pyroprocessing. To gain some vital parameters for electrolysis, simulation is an attractive way to get access to the electrochemical principle. A commercial finite element simulation software COMSOL Multiphisics is used to simulate cyclic voltammetry(CV), chronoamperometry(CA), square wave voltammetry(SWV) and electrodeposited behaviors of CeCl 3 in the LiCl-KCl molten salt. In this work, a comparison of simulation and our experimental data has been utilized to study the electrochemical behaviors of CeCl 3 via CV, CA and SWV. The oxidation-reduction potential of the reaction and the number of transfer electrons were obtained. The electrodeposited behaviors, which consist of the distribution of the current density and potential, concentration distribution of the Ce 3+ , electrodeposited layer distribution were investigated. The influence of temperature, current density and electrodeposited layer density on the electrodeposition is also taken into consideration.