High‐performance self‐lubricating polyphenylene sulfide (PPS)/carbon fiber (CF) composites were obtained by treating the CF surface with heat‐treated cyclic phenylene sulfide oligomers (CPS). The influence of CPS treat conditions on the structure and properties such as mechanical and tribological performance of the composites were studied in detail. The results indicate that the PPS/CPS‐sized CF composites exhibit higher mechanical strength and better tribological performance than the PPS/original CF composites, especially under the condition of higher loads and speeds (300 N × 200 rpm and 200 N × 200 rpm). The performance enhancement is reasonably ascribed to the improved compatibility of the modified CF with the PPS matrix. Further structural analysis reveals that the modified CF treated at 300°C under N2 (CF‐300N) has the most similar structure to the PPS matrix, which makes the comprehensive performances of PPS/CF‐300N composites superior to the products obtained under the other heat‐treatment conditions.