A mass action concentration model of FeO-Fe₂O₃-SiO₂-CaO-MgO-Al₂O₃-ZnO multi-component slag was established to address the problems of high viscosity and high copper content in oxygen-enriched top-blown copper smelting slag. Theoretical calculations, combined with experimental investigations, were performed to evaluate the effects of ZnO additions (0–25 wt.%) on phase transformation, Fe₃O₄ reduction and copper content in the slag at temperatures ranging from 1200 to 1400 °C. The results indicate that ZnO addition decreases the mass concentrations of Fe₂O₃, Fe₃O₄, Fe₂SiO₄ and SiO₂, while increasing the proportions of zinc-bearing structural units and enhancing the reducing capability of the slag. In the copper slag system, Zn²⁺ substitutes for Fe in Fe₃O₄ and Fe₂SiO₄ through isomorphous substitution, forming Fe-Zn spinel and Fe-Zn olivine. As the addition of ZnO gradually increases to 25 wt.%, the liquid slag fraction increases and the slag viscosity decreases, resulting in a reduction in copper content from 5.64 wt.% to 2.04 wt.%. Furthermore, ZnO promotes the transformation of Fe₃O₄ into zinc–iron spinel, which is more readily reducible by carbothermic reaction than Fe₃O₄ itself, thereby facilitating the overall reduction of iron oxides in the copper slag. These findings provide a theoretical basis for slag-type regulation and the efficient separation of copper from slag via high-temperature gravity settling of matte.