<p>To enhance the wear resistance of polyether ether ketone (PEEK)/polytetrafluoroethylene (PTFE) composites, a friction model of PEEK and PTFE with a 1:9 mass ratio was first constructed using molecular dynamics (MD) simulations. Different mass fractions of nano-zirconium dioxide (ZrO₂) were introduced as fillers to improve the wear resistance of the composites. The simulation results demonstrated the superior performance of the PEEK/PTFE composites with 6% ZrO₂ in terms of friction and mechanical properties. The radial distribution function, atomic velocity, relative atomic concentration, and friction interface temperature of the models were analyzed. The results indicated that nano-ZrO₂ enhanced the ability of PEEK/PTFE molecular chains to resist the shear deformation, increasing intermolecular forces within the composite and reducing slippage between molecular chains during the friction process. Composite samples were then prepared, tested, and characterized experimentally, demonstrating the enhancement in wear resistance and mechanical properties of the matrix by adding 6% ZrO₂. This study develops a multi-scale material design paradigm that uses MD simulation at the atomic scale to identify the best ZrO₂ content, explaining the mechanism behind the performance improvements and guiding the experimental fabrication of composite samples at the macroscale.</p>