The aim of the present study is to provide fundamental information regarding the electrochemical formation of Pd-Li alloys and palladium-rare earth alloys in the molten LiCl-KCl system. Pd-Li alloy formation via deposition of lithium onto a palladium electrode in LiCl-KCl eutectic melts was investigated by cyclic voltammetry, open-circuit potentiometry and X-ray diffraction (XRD) analysis. Various phases of Pd-Li alloys, i.e. LiPd7, LiPd2, LiPd and Li2Pd, form at 1.05, 0.64, 0.53 and 0.20 V vs Li+/Li at 450-degrees-C, respectively. The electrochemical window of the molten LiCl-KCl system thus becomes narrow when palladium is used as a cathode.