PEEK is being used increasingly often in seals, bushings, bearings, and other moving parts due to its excellent mechanical and tribological properties. Herein, PEEK-based composites were prepared using PI as the organic filler and h-BN and nano-SiO₂ particles as the inorganic fillers. There was significant improvement in the tribological properties of PEEK at conditions above the glass transition temperature; the coefficient of friction of +20P/4B/4Si was stabilized at 0.06 at 200 °C and the wear rate was reduced by 60% compared to PEEK. The role played by the thermal conductivity of h-BN and the promotion of friction transfer film by nano-SiO₂ in improving the tribological properties of PEEK is illustrated. The modified composites exhibited stable mechanical and tribological properties over a wide temperature range, which is instructive for instrumentation and testing applications in harsh environments.