This study focused on analyzing the changes in the microstructure and composition evolution of plasma electrolytic oxidation (PEO) and electroless copper–PEO composite (Cu/PEO) coatings both prior to and following irradiation. Additionally, the corrosion resistance and tribological properties of these coatings were assessed. Post-irradiation, the PEO coating exhibited a 5% reduction in porosity, and electrochemical impedance spectroscopy (EIS) tests indicated a notable enhancement in short-term corrosion resistance, with a low-frequency impedance of 10⁶ Ω·cm² sustained over 72 h. The Cu/PEO coating, deposited with Bi element, demonstrated enhanced wear resistance after irradiation. Specifically, the coefficient of friction (COF) dropped from 0.7 to 0.5, and the wear rate reduced by 39%.