Waste　enameled　copper　wire　is　an　important　secondary　source　of　copper　and　often　recovered　by　removing　their　organic　paint　layer　through　pyrolysis.　This　research　focused　on　studying　co-pyrolysis　behaviors　of　poly(ethylene　terephthalate)　(PET)　paint　of　waste　enameled　wires,　mixed　with　a　small　amount　of　polyvinyl　chloride　(PVC)　which　is　part　of　electric　wires　or　cables.　The　results　indicated　that　mixing　PVC　with　a　mass　fraction　of　10%　into　enameled　PET　wire　paint　(EPET)　would　significantly　affect　pyrolysis　products,　especially　the　chlorinated　compounds,　as　well　as　increase　energy　consumption　of　the　pyrolysis　process.　TG-FTIR　and　Py-GC/MS　analyses　showed　that　the　chlorinated　organics　were　mainly　generated　in　the　second　stage　of　pyrolysis.　Chloroesters　such　as　terephthalic　acid,　di(2-chloroethyl)　ester　were　dominant　over　other　chloroorganic　compounds,　and　their　formations　were　attributed　to　the　addition　reaction　of　aromatic　vinyl　esters　with　HCl　which　formed　from　PVC　pyrolysis.　It　is　also　worth　mentioning　that　the　chemically　active　acid　chlorides　including　propanoyl　chloride　and　benzoyl　chloride　were　detected　in　the　products,　and　they　were　proposed　to　be　formed　from　the　HCl　acidolysis　of　esters　that　produced　from　pyrolytic　EPET.　Besides　pyrolysis　products,　energy　consumption　of　pyrolysis　process　also　was　closely　correlated　to　the　interactions　between　pyrolytic　PVC　and　EPET.　The　average　co-pyrolysis　activation　energy　was　calculated　by　Kissinger-Akahira-Sunose　(KAS)　method　and　was　about　15　kJ/mol　higher　than　that　of　EPET.　These　should　be　consequences　of　reactions　between　HCl　and　EPET.　Since　PVC　is　the　minority　component　in　the　pyrolysis　mixture　that　HCl　eliminated　from　the　few　PVC　was　mostly　consumed　by　EPET　to　form　chloroorganic　compounds,　which　negatively　influences　EPET　degradation.　©　2022　Elsevier　B.V.