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A combination of waste acid leaching and CaO roasting methods was investigated to recover copper from refining slags of copper fire anode furnace and other valuable metals. The influences of the leaching temperature, leaching time, liquid-solid ratio, and airflow rate on the recovery rates of Cu, Fe, and As were separately evaluated during the leaching process. The roasting temperature, roasting time, and CaO-slag ratio on the removal rates of Cu, Fe, and As were also investigated during the CaO roasting process. The results show that at a leaching temperature of 90 ℃, the liquid-solid ratio of 9:1, leaching time of 4 h, and an airflow rate of 200 mL/min, the leaching rates of Cu, Fe, and As could reach 85.32%, 68.41%, and 44.97% respectively during the waste acid was directly leached from the refining slags of copper fire anode furnace. After leaching, the slags were mixed with CaO under conditions involving a roasting temperature of 800 ℃, roasting time of 4 h, and a CaO-slag ratio of 5.1. After baking, sands were again leached by waste acids: the leaching rate of Cu in baking sands reached 87.05%. The final recovery rates of Cu, Fe, and As could reach 98.10%, 69.60%, and 50.48% respectively. [ABSTRACT FROM AUTHOR]