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Nanoparticles are increasingly being used to improve the friction and wear performance of polymers. In this study, we investigated the tribological behavior and energy dissipation characteristics of nano-Al2O3-reinforced polytetrafluoroethylene-polyphenylene sulfide (PTFE-PPS) composites in a sliding system. The tribological behaviors of the composites were evaluated under different normal loads (100–300 N) at a high linear velocity (2 m/s) using a block-on-ring tester. Addition of the nano-Al2O3 filler improved the antiwear performance of the PTFE-PPS composites, and the friction coefficient increased slightly. The lowest wear rate was obtained when the nano-Al2O3 content was 3% (volume fraction). Further, the results indicated a linear correlation between wear and the amount of energy dissipated, even though the wear mechanism changed with the nano-Al2O3 content, independent of the normal load applied.