The treatment of smelting slag has attracted much attention nowadays. This study investigates the influence of Na2S, CuSO4, and FeCl3 on sulphidizing flotation of copper oxide. The results show that a proper Cu2+ concentration can increase the sulphidizing effect of copper oxide, while Fe3+ inhibits the sulphidizing effect. Further analysis shows that Cu2+ ions can reduce the surface potential, increase the S2− adsorption, then generate more polysulfide, and therefore promote the sulphidizing flotation. However, Fe3+ ions would increase the surface potential, reduce the S2− adsorption, generate more sulfur element, and therefore inhibit the sulphidizing flotation.