For　the　recovery　of　enameled　wire,　pyrolysis　is　a　resource-friendly　and　effective　process.　However,　because　waste　enameled　wires　are　typically　recovered　from　e-waste,　a　minor　number　of　wires　and　cables　are　usually　present.　As　a　result,　co-pyrolysis　of　the　paint　film　and　wire　and　cable　sheaths　is　inevitable　during　the　pyrolysis　recovery　of　waste　enameled　wires.　Polyethylene　terephthalate　(PET)　polyester　enameled　wire　and　polyvinyl　chloride　(PVC)　were　chosen　as　representatives　of　enameled　wire　and　cable　sheath　materials,　respectively.　The　pyrolysis　characteristics　and　pyrolysis　kinetic　parameters　of　enameled　PET　(EPET)　wire　paint,　PVC,　and　Mixture　(a　mixture　of　the　two　materials,　mEPET:　mPVC　=　9:1)　were　investigated　using　TG　and　various　kinetic　analysis　methods.　The　combined　pyrolysis　index　and　Py-GC/MS　were　used　to　assess　the　co-pyrolysis　of　EPET　and　PVC　and　the　products.　The　pyrolysis　of　EPET　is　adversely　affected　by　the　presence　of　PVC　throughout　the　process;　however,　the　presence　of　Cu　in　EPET　may　facilitate　the　HCl　removal　reaction　of　PVC.　The　co-pyrolysis　products　of　EPET　and　PVC　are　more　complex,　and　according　to　the　different　main　functional　groups,　can　be　divided　into　monocyclic　aromatic　hydrocarbons,　polycyclic　aromatic　hydrocarbons,　phenols,　ketones,　aldehydes,　alcohols,　esters,　carboxylic　acids,　chlorides,　and　others.　Finally,　density　functional　theory　calculations　were　used　to　explore　the　co-pyrolysis　mechanism　of　PET　and　PVC　as　well　as　the　creation　mechanism　of　various　pyrolysis　products.　The　catalytic　mechanism　of　Cu　contained　in　EPET　on　PET　and　PVC　was　explained　from　the　perspective　of　electrostatic　potential.　This　study　provides　a　theoretical　foundation　and　comprehensive　reference　for　the　pyrolysis　and　recycling　of　waste　enameled　wires.　©　2024　Elsevier　Ltd