Polymer composites served in marine engineering are typically subjected to severe lubricating challenges due to the low seawater viscosity. In this study, tribochemical reactive SiC whiskers were incorporated in the polytetrafluoroethylene (PTFE)/polyetherketon (PEK) composite. The chemical composition, microstructure and formation process of the transfer film as a function of the whisker amount were evaluated. The results showed that 0.5% SiC whiskers facilitated transfer film formation, resulting in the highest thickness of 94   nm and decreasing the wear rate to 2.9×10 -6 mm 3/N·m. By using SiC whiskers as tribochemical reaction sites together with PTFE microparticles, a protective transfer film with a modulus of 1.5   GPa was constructed, reducing the wear of the polymer composites and limiting seawater corrosion of their metallic counterparts.