Abstract: This is an article in the field of metallurgical engineering. The preparation of black copper electrolyte by removing copper from secondary refining slag of high copper and high tin anode furnace by hydrogen peroxide oxidation and acid leaching was studied. The process conditions related to the removal efficiency of the copper and arsenic were researched including the hydrogen peroxide dosage, reaction temperature, sulfuric acid concentration and reaction time. Results show that, under the following optimal conditions, including refining slag of 20.0 g, 2.5 mol/L sulfuric acid of 200 mL, solid-liquid ratio of 1/10, temperature of 65 ℃, dosage of hydrogen peroxide of 10.0 mL, stirring speed of 400 r/min and leaching time of 60 min, the leaching ratios of Cu and As can reach 88.98% and 87.33%, respectively, and the leaching ratios of Ni and Sn were only 7.72% and 1.34%, respectively. The concentration of copper ion in the leaching solution was 48.48 g/L, which can be used as the supplement of black copper electrolyte.