Due to growing concern over environmental impacts and the pressure to lower carbon footprints in the metals industry, hydrogen (H2) has gained attention as a promising alternative for the replacement of carbon as a reductant and fuel. This paper evaluates the potential use of hydrogen as an energy source and reducing agent during the processing of waste printed circuit boards (waste PCBs) from e-waste through black copper smelting. The effect of the use of carbon and hydrogen during the reduction−oxidation process was analysed and compared from the perspective of thermodynamics and heat balance. The thermodynamic analyses of waste-PCB processing were carried out using the FactSage thermochemical package for the smelting process at temperatures from 1473 K to 1673 K (1200−1400 °C). The results show that the CO2 emissions can be reduced by 73% when hydrogen is used as the reducing agent. A minimum of 10 wt% of waste PCBs in the feed material can be used to replace the necessary carbon to supply heat for the reduction process. The addition of waste PCBs can increase the volume of slag and affect the composition of the off gas.