Cyclic voltammetry (CV), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) were employed to investigate the electrodeposition of Eu and Al in an LiCl–KCl eutectic melt containing Eu 2+ and Al 3+ at 450°C. In order to deposit a pure Eu and Al alloy, the stoichiometrically lower concentration of Al 3+ than that of Eu 2+ and Al wires as a counter electrode was introduced into the bath of LiCl–KCl melt for the electrodeposition. The electrodeposition takes place at a potential more negative than −1.95V vs. Ag|Ag + while the deposit is oxidized at more positive potential than −1.92V. Two new reduction peaks and an anodic peak on a W working electrode were observed at −2.39V, −2.42V, and −2.1V, vs. Ag|Ag + , respectively, suggesting that the potential window of the Al system in LiCl–KCl melt can be extended to −2.43V vs. Ag|Ag + . The EDS analysis indicated that AlEu can be deposited at the potential more negative than −2.37V.