This study examined the high-temperature stability of polyether ether ketone (PEEK) and polyphenylene sulfide (PPS) in an oxygenated environment. Both polymers were extrusion-coated onto copper wires for electrical insulation in traction motors. Accelerated testing using thermogravimetry and calorimetry showed that copper catalyzed thermal oxidation of PEEK (at very high temperature), which was accelerated by a lower molar mass of the PEEK and an increased copper-polymer contact area. Both techniques indicated a complex thermal oxidation pattern for both polymers. Notably, the presence of copper seemed to reduce/retard the degradation of PPS. Overall, both polymers demonstrated high oxidation resistance at elevated temperature in an air environment, indicating long service life in electric motor, excluding factors like moisture, oil spray cooling and Joule heating.