AbstractCarbon fiber reinforced polyether ether ketone (CF/PEEK) composites are widely used as tribo‐materials in the aerospace and automotive industry. To amplify the industrial utilization of extrusion‐based additive manufacturing fused deposition modeling in fabricating CF/PEEK tribo‐composites, the composites' microstructure–property relationship was studied with respect to carbon fiber content varying between 5 wt% and 30 wt%. This revealed that the incorporation of carbon fibers helped enhance the mechanical strength of PEEK greatly with an optimal content of 5 wt%, at which the composite material exhibited the highest crystallinity as well as the best mechanical performance. Tribological tests indicated that CF/PEEK composites were more suitable for high speed and heavy load conditions especially for 20 wt% CF/PEEK, which was associated with the establishment of high quality transfer films covered on counter steel surfaces. The present work provides a simple and low cost way of fabricating high performance PEEK composites used as tribo‐materials. © 2024 Society of Industrial Chemistry.