The 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 were studied. 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 demonstrates 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 manifest 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.