Incorporating impuritiesImpurity, particularly from the recyclingRecycling of e-scrap, may significantly impact the electrorefining processElectrorefining process of the anodesAnode from a copper smelterCopper smelter. In this study, commercial anodesAnode were doped with Ni, Sn and Sb to achieve concentrations of 2500–6500 g/t, 300–900 g/t and 450–950 g/t, respectively. Electron microscopy with microprobe analysisAnalysis revealed that the doped anodesAnode contained NiO, Kupferglimmer and SnO2, which were not present in the original commercial anodesAnode. Ni, the main impurityImpurity, primarily accumulated within the Cu grains, while Sn and Sb tended to form oxidized inclusions. The distributionDistribution of Ni in Cu grains was ca. 20% lower in the anodesAnode doped at higher Ni concentrations due to the formationFormation of nickelNickel-bearing inclusions, such as Kupferglimmer and NiO. The doped anodesAnode showed lower quantities of Cu2O inclusions than the commercial anodesAnode due to the preferential formationFormation of oxides with these added impuritiesImpurity. X-ray diffraction of the slimes collected after electrorefiningElectrorefining the doped anodesAnode in a small laboratory cell using commercial electrolyteElectrolyte revealed that new phases generated in the casting process deported to the slimes. These findings highlight potential challenges for Cu electrorefiningElectrorefining in a circular economyCircular economy, as increased Ni, Sb and Sn content will impact the composition of slimes and electrolyteElectrolyte.