Strongly acidic wastewater, which is usually generated from nonferrous metal smelting industries, has the ability to be recycled as sulfuric acid. Before this wastewater is recycled, the removal of chloride ions is necessary to improve the quality of the recycled sulfuric acid. At present, the widely used method to remove chloride ions from acidic wastewater in the form of CuCl precipitate has several disadvantages, including low removal efficiency, high temperature, long treatment time, and high dosage of Cu(II). This study proposed an improved new method of removing Cl(-I) using Cu(0)/Cu(II) under UV irradiation, and the mechanism was investigated. The Cl(-I) concentration was lowered to below 50 mg/L at a Cu(II) dosage of 1200 mg/L. Under UV irradiation, ligand-to-metal charge transfer takes place, thereby resulting in the formation of Cl•. Next, CuCl precipitates form through the reaction between Cu(0) and Cl• and produce h+/•OH under UV irradiation, which can oxidize Cl(-I) to Cl•. Simultaneously, Cl2 gas also forms directly from Cl•. This study offered a theoretical foundation for the application of UV irradiation for the enhanced removal of chloride ions from strongly acidic wastewater.