In this paper, the electrochemical behaviors of Pb(II) and Pr(III) were investigated on W electrode in LiCl–KCl melts, respectively. The results illustrated that the reduction of Pb(II) and Pr(III) was a one step process. When the PbCl 2 and PrCl 3 co-existed in the molten salt, the cyclic voltammetry, square wave voltammetry and open circuit chronopotentiometry illustrated that four kinds of Pb-Pr intermetallic compounds were formed at 773 K. Whereafter, the electrochemical behavior of Pr(III) on liquid Pb cathode was studied by cyclic voltammetry in LiCl–KCl melts, and the result showed that only one kind of Pb-Pr intermetallic compound was formed at 773 K. The Pr element was extracted by galvanostatic and potentiostatic electrolysis with the assistance of Pb cathode in LiCl–KCl–PrCl 3 melts, respectively. Finally, the obtained alloys were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS), and the result illustrated that the prepared intermetallic compound mainly is Pb 3 Pr.