The escalating demand for refined copper intensifies research into the recycling of copper-based solid waste, exemplified by recovery of copper from waste enameled copper wires (WECWs). Despite its potential, the pyrolysis process for WECWs is hindered by embrittlement, diminishing both recycling yield and quality. Our study pioneers the elucidation of the embrittlement mechanism during WECWs pyrolysis through atom probe tomography and first-principles calculations, revealing that hydrogen, a byproduct of paint film pyrolysis, accumulates at copper grain boundaries, inducing embrittlement by reducing adhesion energy. We introduce two innovative strategies to mitigate hydrogen-induced embrittlement: vacuum pyrolysis and enhanced N2 flow. These approaches significantly reduced hydrogen content from 11.1 % to about 5 % and increased elongation from 2.65 % to 15 %. Moreover, pyrolysis efficiencies of 92.79 % and 91.4 % were achieved, respectively, at temperatures 50 °C lower than conventional methods. Our findings provide crucial theoretical insights into embrittlement and offer effective recovery strategies for copper from solid waste.