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This study investigates the effects of electron irradiation on the structural, surface energy, and tribomechanical properties of two key thermoplastics: polyetheretherketone (PEEK) and polytetrafluoroethylene (PTFE). The experimental methods included electron beam irradiation using the ILU-10 pulsed linear accelerator, Fourier transform infrared spectroscopy (FT-IR), x-ray diffraction (XRD), microhardness testing, surface roughness assessment, tribology tests, and contact angle measurements.The FT-IR analysis revealed significant chemical changes on the surfaces of the polymers, including oxidation processes and the breaking of molecular bonds. XRD analysis showed an increase in the crystallinity of PTFE after irradiation, while the structure of PEEK remained stable. Microhardness testing indicated a notable increase in hardness for both polymers, particularly for PTFE, suggesting cross-linking of molecular chains. Surface roughness measurements demonstrated a decrease in roughness for both irradiated polymers. Tribology tests revealed that electron irradiation increased the coefficient of friction for PTFE and PEEK under various loads, which can be attributed to the alterations in their surface properties. Contact angle measurements indicated improved wettability of the irradiated surfaces, especially for PEEK, due to the formation of new functional groups. The total surface energy increased for both polymers post-irradiation, as determined using the Owens-Wendt-Rabel-Kaeble method. Electron irradiation leads to significant modifications in the surface and bulk properties of PEEK and PTFE, enhancing their tribomechanical and adhesive properties. These changes open new opportunities for the application of these materials in various engineering fields where specific performance characteristics are required.