Polytetrafluoroethylene (PTFE) was irradiated with protons in a ground-based simulation facility to study the effects of proton irradiation on the structural and tribological properties of PTFE. The structural changes were characterized by X-ray photoelectron spectroscopy (XPS) and attenuated total-reflection FTIR (ATR-FTIR), while the tribological properties were evaluated by friction and wear tests. It was found that proton irradiation induced the degradation of PTFE molecular chains, resulting in the increase of C concentration and the decrease in F concentration on the sample surfaces, and the surface chemical structure and morphology of the samples changed, which affected the friction coefficient and decreased the wear rate of the specimens as the friction and wear tests revealed.