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• Studies partial discharge induced thermal decomposition of composite insulator epoxy. • Analyzes 200–1000 °C pyrolysis products of anhydride-cured bisphenol A epoxy resin. • Crosslinking points cleave below 360 °C; epoxy main chains break above 380 °C. • Formed gases, swelling-induced liquids and acids can impact insulator components. • Proposes product formation mechanisms and mitigating strategies to their effects. Epoxy/anhydride thermoset matrix within composite insulator core rods may thermally decompose by temperature rise caused by partial discharge. The thermal decomposition characteristics of the epoxy/anhydride thermoset was analyzed using pyrolysis-gas chromatography-mass spectrometry (PY–GC–MS) from 200 to 1000 °C, including the mechanisms of crosslinked network scission and the formation of gaseous or liquid products with potential secondary effects on surrounding materials. Below 360 °C, scission at crosslinking points predominates by ceiling temperature behavior, forming anhydrides. Above 380 °C, scission of main chains leads to the production of corresponding fragments. Beyond 600 °C, decomposition of anhydrides and fragments from main chains leads to the formation of lower molecular weight substances. During the pyrolysis process, organic acids are formed from 240 °C to 1000 °C. Above 600 °C, gases with high vapor pressures and liquids that can induce swelling are produced. These byproducts can have secondary effects on surrounding materials, including the failure of interfacial adhesion, swelling of silicone rubber sheaths, and a reduction in the mechanical strength of glass fibers. Consequently, these effects may accelerate the decay-like deterioration of core rods, characterized by a surface morphology reminiscent of rotting wood. These findings will inform the optimization of materials for enhanced electrical equipment performance and facilitate the evaluation of potential environmental impacts posed by the thermal decomposition of epoxy/anhydride thermosets in future applications. [ABSTRACT FROM AUTHOR]