Pyrolysis　technology　is　a　green　and　efficient　method　for　recycling　enameled　wires.　However,　since　waste　enameled　wires　are　typically　recovered　from　electronic　waste,　they　often　contain　small　amounts　of　wires　and　cables.　Therefore,　during　the　pyrolysis　process　of　waste　enameled　wires,　it　is　inevitable　for　the　paint　film　and　the　cable　sheath　to　undergo　co-pyrolysis.　Polyesterimide　enameled　wires　(EPEsI)　and　polyvinyl　chloride　(PVC)　were　chosen　as　represent　enameled　wires　and　cable　sheath　materials,　respectively.　Using　thermogravimetric　analysis　with　various　pyrolysis　kinetic　analysis　methods,　the　pyrolysis　characteristics　and　kinetics　of　EPEsI　and　Mixture　(mixture　of　EPEsI　and　PVC)　were　studied.　Through　synergy　analysis　and　pyrolysis-gas　chromatography/mass　spectrometry　analysis,　the　influence　of　PVC　on　the　pyrolysis　of　EPEsI　was　elucidated　from　aspects　such　as　pyrolysis　characteristics　and　product　distribution.　Based　on　density　functional　theory　calculations　and　wave　function　analysis,　the　role　of　endogenous　metal　Cu　in　EPEsI　on　the　pyrolysis　processes　of　PEsI　and　PVC,　as　well　as　the　mechanism　of　HCl　from　PVC　on　the　pyrolysis　of　PEsI,　were　clarified.　©　2024　The　Authors