Galena and chalcopyrite pose challenges in their separation owing to their similar surface chemistry. The flotation separation of galena and chalcopyrite significantly depends on the use of depressants. However, conventional depressants are often associated with several drawbacks, such as toxicity and inefficiency. Hence, exploring efficient and environmentally friendly techniques to separate galena and chalcopyrite is vital. This study investigated the use of sulfuric acid as a surface oxidant for the pre-oxidation treatment of galena and chalcopyrite at high temperatures. This approach facilitated acid recycling and eliminated the need for multiple flotation chemicals. The floatability of galena and chalcopyrite was investigated through micro-flotation. The results revealed that at a pre-oxidation temperature of 100℃, galena exhibited a recovery rate of only 9.98 %, while chalcopyrite maintained a recovery rate of 96 % across the temperature range. The selective depressant mechanism of sulfuric acid in the flotation separation of galena and chalcopyrite was investigated through scanning electron microscopy, zeta potential measurements, X-ray photoelectron spectroscopy, thermodynamic calculations, and electrochemical analyses. The results indicated that the high temperature facilitated the dissolution of the sulfide layer on the galena surface. Consequently, S2− ions underwent oxidization into SO42− to form a stable oxide film on the galena surface through interaction with Pb2+. Conversely, the high-temperature pre-oxidation had a minimal effect on the surface of chalcopyrite, indicating selective oxidation benefits. Findings from the pre-oxidation floatation separation test of galena–chalcopyrite mixtures revealed the efficient and thorough separation of the two minerals under high-temperature pre-oxidation conditions. The lead concentrate obtained from the floatation process exhibited a Pb grade of 79.38 % and a recovery rate of 97.17 %, while the Cu concentrate featured a Cu grade of 32.14 % and a recovery rate of 97.06 %. Additionally, the sulfuric acid solution was recycled. Overall, this study provides a sustainable and cost-effective approach for the green separation of copper–lead sulfide ores.