Abstract: Copper electrorefining is key to removing impurities and improve purity in cathode copper production. At the same time, additives are the key factors affecting the surface quality and purity of cathode copper during electrolysis. In this paper, the effects of four kinds of additives, including chloride ion, amine organic matter, sulfur-containing organic matter, and polyether organic matter, in the copper electrorefining process and the synergies between various additives were reviewed. The research on additives for copper electrorefining was analyzed, summarized, and prospected, which is of great significance for developing such kind of new additives and the green development of the copper electrolysis industry.