Electrochemistry plays an essential role in modern technologies of energy conversion, metals production/recovery, and corrosion-resistant materials. A proper control of electrode reactions in a complex environment is an important consideration for the successful development of future sustainable electrochemical technologies. Today, rare-earth metals are produced by electrolytic reduction in molten salts and play a critical role for the transition to a green, low-carbon economy because of their essential role in renewable energy technologies such as permanent magnet (NdFeB) motors for electric vehicles and wind turbines. This presentation will discuss electrochemical processes for rare-earth alloys (e.g., Nd-Bi and Nd-Fe) in molten salts with a specific focus on fundamental challenges of rare-earth electrochemistry (e.g., high reactivity and multivalent states) that can lead to low process yield. As a first step to understanding electrode processes of rare-earth alloys in molten salts, thermochemical properties of rare-earth alloys (e.g., Nd-Bi and Nd-Fe) were investigated via electromotive force (emf) measurements in complement with characterization of alloy electrodes via thermal and microstructural analyses. Based on the emf of these alloys, the electrochemical formation of these alloys is demonstrated in molten salts with an estimation of the process efficiency.