For the tribological properties of nanoparticle-modified PTFE, a more comprehensive study has been conducted, but there is still some room for research on tribology behavior, tribofilm formation and structure evolution of polytetrafluoroethylene (PTFE) filled with α-Al₂O₃ and SiO₂ nanoparticles during sliding against steel counterparts under different loads. At the same time, it establishes the linkage and mechanism between the maintenance of mechanical strength and the tribological application of polymers in service and provides corresponding scientific data and theoretical guidance for the long-lasting application of polymer lubrication materials. It is found that both composites exhibit good wear resistance across the pressure of 1 MPa to 10 MPa, with the α-Al₂O₃/PTFE composite demonstrating better performance stability compared to the SiO₂/PTFE composite. The high wear resistance is attributed to the formation of tribofilms at the friction interface. For the α-Al₂O₃/PTFE, an island-like tribofilm is formed with a thickness ranging from 100 to 200 nm, while the tribofilm of the SiO₂/PTFE composite is thinner, measuring approximately 50 to 100 nm, and manifests a striped pattern. The chemical composition, both at the surface and subsurface levels, as well as the morphology of the tribofilms, were studied using FTIR spectrometry, X-ray photoelectron spectroscopy (XPS), and FIB-TEM. It is found that the difference in thickness and microstructure of the tribofilms for the two composites is mainly due to the tribochemistry of the nanoparticles. The α-Al₂O₃ nanoparticle plays a “cohesion” role during the formation of the tribofilm, which facilitates the formation of a thicker, more uniform, and stronger adhered tribofilm on the metallic counterpart, making it more robust against higher shear stress.