Ultrahigh-Ni layered cathodes are among the most promising materials for next-generation lithium-ion batteries due to their high energy density, but their practical use is often limited by severe surface instability and structural degradation. In this work, surface Co doping of LiNi0.93Co0.05Al0.02O2 (NCA) is demonstrated to enhance both electrochemical performance and structural stability. The introduction of Co at the surface promotes the formation of stable spinel phases, such as Co3O4 and LixCoO2, which simultaneously remove residual lithium species and suppress the evolution of detrimental NiO-like rock-salt phases and resistive interfacial layers. Comprehensive analyses, including electrochemical testing, synchrotron-based X-ray techniques, and high-resolution electron microscopy, confirm that Co-doped NCA exhibits improved interfacial stability and lithium-ion transport compared to undoped NCA. These findings highlight surface Co doping as a scalable and practical design strategy to mitigate degradation pathways, thereby enabling ultrahigh-Ni cathodes to achieve greater durability and performance in advanced lithium-ion battery applications.