The dissolution mechanism of CeO₂ in molten CeF₃–LiF–BaF₂ and the electrochemical behavior of Ce(III) on molybdenum electrode in molten CeF₃–LiF–BaF₂ were investigated. Cyclic voltammetry, chronoamperometry and potentiostatic electrolysis were performed to investigate the reduction mechanism of Ce(III) ions. The products obtained by dissolution reaction and potentiostatic electrolysis were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The results show that CeO₂ can dissolve into the fluoride molten salts in the form of CeOF, by reacting with CeF₃. Further, cerium oxyfluorides can be directly reduced to cerium metal with a purity of 99.38–99.81 wt% on molybdenum electrode via a reversible three-electron-transfer process, which is controlled by diffusion.