Exergy analysis is one of the useful decision-support tools in assessing the environmental impact related to waste emissions from fossil fuel. This paper proposes a thermodynamic-based design to estimate the exergy quantity and losses during the recycling of copper and other valuable metals out of electronic waste (e-waste) through a secondary copper recycling process. The losses related to recycling, as well as the quality losses linked to metal and oxide dust, can be used as an index of the resource loss and the effectiveness of the selected recycling route. Process-based results are presented for the emission exergy of the major equipment used, which are namely a reduction furnace, an oxidation furnace, and fire-refining, electrorefining, and precious metal-refining (PMR) processes for two scenarios (secondary copper recycling with 50% and 30% waste printed circuit boards in the feed). The results of the work reveal that increasing the percentage of waste printed circuit boards (PCBs) in the feed will lead to an increase in the exergy emission of CO2. The variation of the exergy loss for all of the process units involved in the e-waste treatment process illustrated that the oxidation stage is the key contributor to exergy loss, followed by reduction and fire refining. The results also suggest that a fundamental variation of the emission refining through a secondary copper recycling process is necessary for e-waste treatment.