This work presents the electrochemical deposition of Mg-Pr and Mg-Li-Pr alloys on tungsten electrodes in molten LiCl-KCl-MgCl2-PrCl3 system. The electrochemical behavior of Mg(II), Pr(III), and Li(I) ions and alloy formation process in the melts were investigated by cyclic voltammetry (CV) and open circuit chronopotentiometry (OCP). Spherical bulk alloys were obtained by potentiostatic and galvanostatic electrolysis at -1.85V for 3h and -6.00A cm(-2) for 2h, respectively. Pr and Li contents in the alloys were regulated by changing the concentration of PrCl3 and MgCl2 in the melts. The proportion of Pr was controlled from 9.73 to 19.93 wt.% in Mg-Pr alloys and the ratio of Li changed from 0.10 to 37.27 wt.% in Mg-Li-Pr alloys. X-ray diffraction (XRD) indicated that Mg-Pr alloys were solely comprised of alpha-Mg and Mg12Pr phases. However, in Mg-Li-Pr alloys, the phases were transformed from Mg12Pr to Mg3Pr, accompanied by the transition of matrix (from alpha-Mg to beta-Li). The microstructure and micro-zone chemical analysis of Mg-Pr and Mg-Li-Pr alloys were characterized by scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS). (C) 2013 Elsevier Ltd. All rights reserved.