High‐performance polymer nanocomposites based on poly(aryletherketone) (PAEK) as matrix and hexagonal boron nitride (h‐BN) nanopowder as reinforcement were fabricated using planetary ball mill followed by hot pressing. The addition of h‐BN (0–5 wt %) to the matrix enhanced the microhardness and thermal stability compared to pure matrix. For a constant sliding speed, the wear rate of the nanocomposites determined by using Pin‐on‐Disk tribometer was reduced approximately 22 times compared to pure matrix. The coefficient of friction of the nanocomposites is slightly increased but it is stable compared to that of pure matrix. It was also investigated that the thermal stability of the debris of the nanocomposites was decreased compared to the pure matrix and its nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44409.