<p>Tb is a rare earth element that has excellent properties for use in various industries. However, its recovery and recycling are hindered by the thermochemical reduction process currently being used. Therefore, an alternate process is required. Molten salt electrolysis is used for other rare earth elements such as Dy; however, the typical product is an alloy, and Tb alloys have low commercial value. Therefore, we propose a novel recovery process wherein a purified Tb compound is subjected to molten salt electrolysis with a volatile metal cathode so that a liquid Tb alloy forms at the cathode, followed by volatile separation and vacuum melting of the alloy to obtain metallic Tb. The selection of an appropriate volatile metal is crucial because it determines the available temperature ranges for the process, which in turn impact costs and safety; we identified Zn and Mg as the most suitable based on thermodynamic data such as vapor pressures and enthalpies for mixing. We then formed a Tb-Zn alloy by molten salt electrolysis and heated it under vacuum. The resulting product was a metallic Tb ingot with a purity of &gt; 98.0 mass%. This indicates that the proposed process is viable for the recovery of high-purity Tb metal.</p>