<p>Copper is a strategic metal that plays an important role in many industries. In copper metallurgy, electrolytic refining is essential to obtain high-purity copper. However, during the electrolytic refining process, impurities such as arsenic are introduced into the electrolyte, which significantly affect the subsequent production and quality of copper products. This paper first discusses the sources, forms, and transformation pathways of arsenic in copper electrolyte during the electrolytic process, then reviews various arsenic removal technologies in detail, including electrowinning, adsorption, solvent extraction, ion exchange, membrane filtration, and precipitation. Particular emphasis is placed on electrowinning, which is the most widely used and mature among these arsenic removal techniques. The paper evaluates these methods based on arsenic removal efficiency, cost effectiveness, technical maturity, environmental friendliness, and operation simplicity. In addition, the paper explores future trends in copper electrolyte purification, focusing on waste reduction at source, resource utilization, intelligent digitalization, and innovations in materials and processes. This review aims to provide researchers and practitioners with a comprehensive and in-depth reference on arsenic removal methods in copper electrolytes.</p>