In this study, poly (ether ether ketone) (PEEK)/polytetrafluoroethylene (PTFE) composites reinforced with carbon fibers (CFs) and graphite (Gr) were fabricated by compressive molding technology. The friction and wear properties of the PEEK/PTFE composites sliding against Si₃N₄ balls were investigated using ball-on-disk configuration under dry sliding conditions, and the morphologies of the worn surfaces were also observed with a scanning electron microscope (SEM) and a three-dimensional morphometer. The results indicated that the introduction of CFs significantly improved the tribological properties of the composites, but the friction coefficient of the PEEK/PTFE/CFs composites were higher than the pure PEEK/PTFE composites. However, it was found that a combinative addition of CFs and Gr creates an obvious synergetic effect of improving the friction-reducing and anti-wear abilities of the composites. The mechanisms of the improved tribological properties of the PEEK/PTFE/CFs/Gr composites were discussed based on the analysis of the worn surfaces and tribofilms.