Abstract: Aiming at solving the technical problem that the complex copper-lead minerals are difficult to separate efficiently, this paper introduced an acetic acid-sodium acetate electro-oxidation system and systematically investigated the electro-oxidation leaching and separation behavior of galena and chalcopyrite. The results showed that acetic acid-sodium acetate can not only maintain the stability of the system, but also strengthen the selective leaching process of galena by combining with lead ions to form complexes. The optimized process parameters were: solid-liquid ratio 0.02 g/mL, stirring speed 700 r/min, anode current density 659.4 A/m², normal temperature, reaction time 60 min, sodium chloride concentration 3 mol/L, cell voltage 3.8~4.4 V. Under such optimized conditions, the leaching rate of lead reached 71.55%, and that of copper is less than 1.85%, which led to the economical and efficient separation and recovery of lead and copper minerals. This technology has a good industrial prospect in application.