The recycling of waste electronic and electrical equipment (WEEE) and other secondary copper-containing materials through the "black copper" process relies on the selective distribution of metals among the gas, slag, and copper-rich liquid phase. This distribution is controlled by the effective oxidation/reduction potential, often expressed in terms of oxygen partial pressure. Separation of Ni and Sn presents a certain challenge in recycling though black copper route due to similar distribution coefficients over a wide range of oxygen partial pressures and possibly can be improved by optimizing the slag chemistry. This study provides experimental information on the distribution of Ni, Sn, and Zn between fayalite slags or calcium ferrite slags and copper-rich metal at 1250°C. The study uses high-temperature equilibration, quenching, and electron probe X-ray microanalysis (EPMA) techniques along with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for selected measurements of low concentrations. The oxygen partial pressure is controlled by the CO/CO2/Ar gas flow or by measuring the concentration of copper oxide in the slag. The effect of slag composition in terms of Fe/SiO2 or Fe/CaO ratio is studied by using different holding materials, such as silica (SiO2) ampoule, solid spinel (Fe3O4), wüstite (FeO), or dicalcium ferrite (Ca2Fe2O5). The experimental results are compared with literature data and used to optimize thermodynamic models for FactSage® software. The results demonstrate an opportunity for more effective separation of Ni and Sn using at oxidizing stage by using calcium ferrite slag promoting the formation of Sn4+.