The　pyrolysis　treatment　of　waste　polyesterimide　enameled　wire　offers　significant　advantages　such　as　continuous　processing,　non-hazardous　nature,　and　high　resource　recovery　rate.　However,　research　on　its　pyrolysis　process　and　mechanism　remains　insufficiently　explored.　In　this　study,　techniques　including　thermogravimetry　(TG),　Fourier　transform　infrared　spectroscopy(FT-IR),　pyrolysis-gas　chromatography-mass　spectrometry(Py-GC/MS)　were　employed　to　investigate　pyrolysis　temperature,　weight　loss　rate,　pyrolysis　and　kinetic　parameters,　composition　and　distribution　of　pyrolysis　products,　and　changes　in　functional　groups　under　different　temperatures　and　heating　rates.　The　pyrolysis　of　polyesterimide　enameled　wire　can　be　divided　into　three　stages:　volatilization　of　specific　components　(314.8　degrees　C,1.6　%),　rapid　decomposition　of　polyesterimide　(435.2　degrees　C,　44.7　%),　and　generation　of　small　organic　molecules　with　the　fixation　of　pyrolytic　carbon　(750　degrees　C,　9.0　%).　The　main　components　of　the　pyrolysis　gas　products　include　aromatic　compounds,　ethers,　aromatics,　ketones,　and　carbon　dioxide.　At　400　degrees　C,　a　substantial　amount　of　pyrolysis　gas　products　and　free　radicals　are　produced,　with　an　increase　in　aromatic　hydrocarbons.　The　carbon　distribution　in　the　pyrolysis　products　mainly　focuses　on　C6-C10　and　C11-C15,　and　many　organic　compounds　such　as　benzoic　acid,　phenol,　and　aniline　are　generated.　Based　on　density　functional　theory,　the　bond　dissociation　energies　in　the　polyesterimide　were　calculated.　This　clarified　the　possible　thermal　decomposition　pathways　of　the　polyesterimide　and　provided　the　energy　barrier　values,　elucidating　the　generation　mechanism　of　pyrolysis　products　during　thermal　decomposition.　The　copper　atom　in　specific　location　reduces　the　negative　ESP　of　O　and　increases　the　positive　ESP　of　H　in　EPI,　which　makes　H　more　likely　to　attach　to　O.　The　presence　of　Cu　increases　the　ESP　range　and　promote　the　pyrolysis　process.　This　study　provides　a　theoretical　basis　for　the　high-value　recycling　of　waste　polyesterimide　enamelled　wire.