Total joint replacement is currently the most successful clinical treatment for improving the life quality of individuals afflicted with end-stage osteoarthritis of knee or hip joints. However, release of wear and corrosion products from the prostheses is a critical issue causing adverse physiological responses of local issues. β-SiC nanoparticles were dispersed into polyetheretherketone (PEEK) materials and their role in tribocorrosion performance of PEEK-steel joints exposed to simulated body fluid was investigated. It is demonstrated that β-SiC nanoparticles increase greatly the wear resistance of the PEEK materials, and meanwhile mitigate significantly corrosion of the steel counterpart. It is revealed that tribochemical reactions of β-SiC nanoparticles promoted formation of a robust tribofilm having complex structures providing protection and shielding effects. The present work proposes a strategy for developing high-performance polymer-on-metal joint replacement materials of enhanced lifespan and biocompatibility via tuning interface nanostructures. Statement of SignificanceAdverse tissue responses to metal wear and corrosion products from metal base implants remain a challenge to surgeons and patients. We demonstrated that leaching of metal ions and release of metallic debris are well decreased via tuning interface nanostructures of metal-polymer joint bearings by dispersing β-SiC nanoparticles into polyetheretherketone (PEEK). It is identified that the addition of β-SiC greatly improves the tribological performances of the PEEK materials and mitigated corrosion of the steel. Tribo-chemistry reactions of SiC induce the formation of complex structures which provide protection and shielding effects. Nanostructures of the tribofilm were also comprehensively investigated. These novel findings proposed a potential route for designing high performance metal-polymer joint replacement materials.