Both Al and Ga have exhibited excellent performance, respectively, for the An/Ln separation based on molten salt electrolysis, and the Al-Ga composite cathode may have superior properties. Therefore, in this work, the electrochemical behaviors of Ce (III) on the binary Al-Ga electrode were systematically explored by co-reduction of Ce (III), Al (III) and Ga (III) on a W electrode. A new oxidation signal of Al2Ga2Ce ternary intermetallic compound was successfully detected. In addition, for comparison, the co-reduction behaviors of Ce (III) with Al (III) and Ce (III) with Ga (III) on an inert tungsten electrode were also investigated. The results showed that different kinds of alloys are formed on the surface of W electrode. Finally, several typical Ga-Ce and Al-Ga-Ce intermetallic compounds were obtained by potentiostatic electrolysis and the deposited products were characterized by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM) with Energy Dispersive Spectroscopy (EDS). (C) 2019 Elsevier Ltd. All rights reserved.