Electrochemical preparation of Mg-Li-Al-La alloys on inert electrodes was investigated in LiCl-KCl melt at 853 K (580 °C). Cyclic voltammograms (CVs) and square wave voltammograms (SWVs) show that the existence of AlCl3 or AlF3 could promote La deposition on an active Al substrate, which is predeposited on inert electrodes. All electrochemical tests show that the reduction of La3+ is a one-step reduction process with three electrons exchanged. The reduction of La(III)→La(0) occurred at –2.04 V, and the underpotential deposition (UPD) of La was detected at –1.55 V (vs Ag/AgCl). The same phenomena concerning La UPD were observed on two inert cathodes, W and Mo. In addition, Mg-Li-Al-La alloys were obtained by galvanostatic electrolysis on the W cathode from La2O3 in LiCl-KCl-MgCl2-KF melts with aluminum as the anode. X-ray diffraction (XRD) measurements indicated that various phases like the Al2La, Al12Mg17, and βLi phase (LiMg/Li3Mg7) existed in the Mg-Li-Al-La alloys. The distribution of Mg, Al, and La in Mg–Li–Al-La alloys from the analysis of a scan electron micrograph (SEM) and energy dispersive spectrometry (EDS) indicated that the elements Mg, Al, and La distributed homogeneously in the alloys.