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Poly-ether-ether ketone (PEEK) is a great potential thermoplastic in industry and medical treatment and health. In this work, PEEK/graphene oxide (GO) and PEEK/MoS₂ composites were prepared by a novel hot isostatic pressing method. The addition of GO alters the tribological behaviors mechanism; fatigue wear mechanism is predominant to PEEK/GO composites. However, the combination of abrasive and adhesive wear mechanisms is observed for PEEK/MoS₂ composites and PEEK. The reason for this is that the hardness and tensile strength of composites are increased with the appropriate addition of GO. The response time to stable friction state of PEEK/GO and PEEK/MoS₂ composites is reduced in comparison with PEEK, which is conducive to shorten running-in time, reduce the energy consumption, and improve the tribological performances of composites. The addition of GO and MoS₂ can effectively decrease the friction coefficient and wear rate, and the optimal content of GO and MoS₂ was 0.7 wt.% and 15 wt.%, respectively. The results indicate that PEEK/GO and PEEK/MoS₂ are impressive composites that possess super tribological properties.