The synergistic effects of carbon fiber (CF) and polytetrafluoroethylene (PTFE) on the friction and wear behavior of polyarylene ether nitrile (PEN) under dry lubrication condition were studied. According to the scanning electron microscopy (SEM) on the composites' surface after wear, the wear mechanism of the composites under dry sliding condition was analyzed. The research results show that the addition of solid lubricants PTFE and carbon fibers to PEN helps to enhance the properties of friction and wear. The specific wear rate is decreased to 5.7 × 10−7 mm3/N m at a PTFE composition of 5 wt%, which is optimized by 33.4% more than PEN/CF composites. In addition, wear mechanisms are mainly abrasive wear, accompanied by adhesive wear and plowing of the friction ring.