Electrolyte is considered to be one of the key factors affecting electrolysis in the rare earth and their alloys industry. Generally, the fluoride system is chosen as the electrolyte for industrial production. However, the molten salt electrolysis method for fluoride-oxide systems is not well understood and has not been systematically studied at this stage. In order to supplement this part, lanthanum (La) ions have been chosen as the research object in this paper to systematically investigate the preparation of La−Ni alloy from LaF 3 −LiF-CaF 2 −La 2 O 3 molten salt. A series of electrochemical methods were used to investigate the mechanism and kinetic properties of La(III) reduction on W and Ni electrodes. The electrochemical reduction properties and kinetic parameters of La were obtained. La−Ni alloy was prepared by potentiostatic electrolysis, and it was verified by detailed analysis through characterization methods. On this basis, LaNi 5 intermetallic compound was successfully prepared on Ni electrode. This study provides valuable theoretical guidance for the development of La alloy preparation with fluoride salt systems in industry.