Oxidation is a critical factor contributing to material wear and the degradation of conductive performance during current-carrying tribological processes. The present study investigated the composite oxidation mechanisms that occurred during current-carrying rolling in mixed atmospheres containing O₂ and H₂O vapor. The results obtained in a dry N₂/O₂ mixture, humid N₂, and humid N₂/O₂ mixture indicated that the oxidation mechanisms on current-carrying rolling surfaces involved thermal oxidation, tribo-oxidation, and anodic oxidation. XPS analysis confirmed that the primary oxidation product was CuO. Conductive atomic force microscopy (C-AFM) revealed that surface oxidation caused a significant reduction in conductive α-spots, leading to an increase in contact resistance. Contact resistance exhibited a quasi-linear relationship with the surface CuO content. Contact angle measurements and adhesion tests showed that the enhanced hydrophilicity of the oxidized surface and the resulting high adhesion contributed to an increase in the macroscopic friction coefficient. In humid N₂/O₂ with 50% relative humidity (RH), the friction coefficient rapidly exceeded 0.8 when the O₂ content surpassed 25%. Wear morphology analysis demonstrated that this abrupt increase in the friction coefficient induced fatigue wear on the surface. Overall, the present study elucidated the composite oxidation mechanisms during current-carrying rolling and clarified the pathways through which oxidation affected current-carrying tribological performance. These findings may contribute to improved failure analysis and the safe, reliable operation of electrical contact pairs.