Recycling of waste electrical and electronic equipment (WEEE) is attracting increasing attention, due to the presence of valuable metals and the risk of environmental emissions associated with WEEE disposal. In this study, the distributions of trace elements (Ag, Ni, Co, and Sn) between copper alloy and magnetite/wüstite-saturated iron silicate slags were investigated at 1200–1300 °C and PO2 of 10-10-10-6.5 atm, simulating the conditions of WEEE reprocessing through secondary copper smelting and converting. The high-temperature isothermal equilibration experiments were conducted in synthesized magnetite/wüstite crucibles under controlled CO-CO2 atmospheres followed by quenching in an ice-water mixture. The phase compositions and concentrations of the trace elements in copper alloy, magnetite/wüstite, and slag were determined by Electron Probe X-ray Microanalysis and Laser Ablation-High-Resolution Inductively Coupled Plasma-Mass Spectrometry. The distribution coefficients of all investigated trace elements between copper alloy and slag increased with decreasing oxygen partial pressure and increasing temperature. Ag distributed strongly into the copper alloy at all conditions, whereas Co mainly deported into the slag phase. Ni and Sn were concentrated in the alloy at lower PO2 and in the slag at higher PO2. Varying concentrations of Ni, Co, and Sn were also dissolved into the solid magnetite/wüstite phase.