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The cathodic process of cerium(Ⅲ) ions in NaCl-2CsCl melt was studied by cyclic voltammetry and square wave voltammetry with tungsten and gold electrodes at 873 K. The two electroanalytical methods yield similar results. The cathodic process of cerium(Ⅲ) ions consists of two reversible steps: Ce3+ + e-= Ce2+ and Ce2+ + 2e-= Ce. The half wave potentials of Ce3+/Ce2+ and Ce2+/Ce were determined as -2.525 V vs. Cl2/Cl- and -2.975 V vs. Cl2/Cl-, respectively. The diffusion coefficient of Ce3+ was also determined as 5.5 × 10-5 cm2·s-1.