Developing more reliable joint prostheses is crucial for minimizing impact of end-stage arthritis. In this work, SiC-BN hybrid nanoparticles were compounded into PEEK and their roles in tribocorrosion behaviors of PEEK sliding against a 316L steel in simulated body fluid were explored. Our results manifest that the addition of SiC and BN nanoparticles enhances synergistically tribological performance of the friction pairs. Tribofilm growth and tribo-chemistry at the friction interface were thoroughly investigated. It is demonstrated that hydrolysis products of SiC and easy-slippery characteristic of BN released onto the interface endow the tribofilm with shielding and boundary lubrication effects. Hence, when sliding takes place with the PEEK composite filled with SiC/BN hybrids, the friction pairs exhibit high tribological and anti-corrosion performance.