The performance of Li-B alloy as anode for molten salt electrolysis was firstly investigated. The crystalline phase of the prepared Li-B alloy was identified as Li7B6. The potential profile of Li-B alloy anode was monitored during the electrodeposition of Nd3+ onto an LCC (liquid cadmium cathode) in molten LiCl-KCl salt at 500oC. The potential of Li-B alloy was increased from -2.0 V to -1.4 V vs. Ag/AgCl by increasing the applied current from 10 to 50 mA·cm-2. It was found that not only the anodic dissolution of Li to Li+ but also the dissolution of the atomic lithium (Li0) into the LiCl-KCl eutectic salt was observed, following the concomitant reduction of Nd3+ by the Li0 in Li-B alloy. It was expected that the direct reduction could be restrained by maintaining the anode potential higher that the deposition potential of neodymium.