This work presents the electrochemical study of Sm(III) on an aluminum electrode in LiCl-KCl melts at 773 K by different electrochemical methods. Three electrochemical signals in cyclic voltammetry, square wave voltammetry, open circuit chronopotentiometry, and cathode polarization curve are attributed to different kinds of Al-Sm intermetallic compounds, Al2Sm, Al3Sm, and Al4Sm, respectively. Al-Sm alloy with different phase structure (Al2Sm and Al3Sm) could be obtained by the potentiostatic electrolysis with the change of electrolytic potentials and time. Al-Sm alloy containing whiskers (Al4Sm) was obtained by potentiostatic electrolysis (- 2.10 V) on an aluminum electrode for 7 hours with the change of electrolytic temperature and cooling rate in LiCl-KCl-SmCl3 (16.5 wt. %) melts. The XRD and SEM&EDS were employed to investigate the phase composition and microstructure of Al-Sm alloy. SEM analysis shows that lots of needle - like precipitates formed in Al-Sm alloy, and their ratios of length to diameter are found to be greater than 10 to 1. The TEM and electron diffraction pattern were performed to investigate the crystal structure of the needle-like precipitates. The results show that the needle - like precipitates are intermetallic compound whiskers. The micro-hardness test and potentiodynamic polarization test illustrate that the micro-hardness and corrosion property of Al-Sm alloy containing whiskers are remarkably improved in comparison with the Al-Sm alloy without whiskers, respectively. (C) 2015 Elsevier Ltd. All rights reserved.