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Advancements in technologies related to the electrorefining and electrodeposition of metals—as important manufacturing process steps—continue to receive significant attention. Specifically, novel ideas that focus on the development of new approaches to the electrochemical synthesis of alloys and composites are important for advancing technologies that can promote increased supply sustainability in the future. This Special Issue, “Advances in understanding metal electrolysis process”, aims at the fundamental level of research with respect to novel approaches in areas of electrolysis and electrochemical mechanisms as well as their impact on the efficiency and quality of metal deposition. It consists of ten papers addressing various issues and their possible solutions around the electrolysis/-deposition of aluminum, copper, indium, rare earth metals, and their alloys, including Zn-Co coatings. One review paper provides an overview of the structure of metal powders produced by electrochemical methods.