This work investigates the effects of electron irradiation on the structural, surface energy, and tribomechanical properties of two key thermoplastics: polyetheretherketone (PEEK) and polytetrafluoroethylene (PTFE). This paper describes the experimental methods and research results aimed at assessing changes in the tribomechanical properties, surface roughness, microhardness, structure, and chemical composition of these polymers following electron beam treatment. The results show that electron irradiation leads to significant changes in the surface and bulk properties of the studied thermoplastics. Electron irradiation increases the coefficient of friction for PTFE and PEEK under various loads by altering their surface properties. A decrease in surface roughness and an increase in microhardness, particularly notable for PTFE, were also observed, indicating the key role of cross-linking of molecular chains in increasing the material's hardness. X-ray diffraction demonstrated an increase in the crystallinity of PTFE after irradiation, while the structure of PEEK remained stable. Infrared spectroscopy revealed chemical changes on the surface of the polymers, including oxidation processes and the breaking of molecular bonds. The study of contact angles and surface energy showed an improvement in the wettability of irradiated surfaces, especially for PEEK, which may be attributable to the formation of new functional groups. These changes in surface and bulk properties open up new opportunities for the use of PTFE and PEEK in various engineering applications where specific tribomechanical and adhesive properties are required.