[en] Layered oxide cathodes with a high-nickel (Ni ≥ 0.9) content exhibit great potential for enabling high-energy-density lithium-ion batteries. However, their practical feasibility and cycle life are hampered by severe surface reactivity with the electrolyte. A LiNi${}_{0.90}$Co${}_{0.05}$Al${}_{0.05}$O${}_2$ cathode is presented enriched with Al on the surface (S-NCA) and benchmark it against a LiNi${}_{0.90}$Co${}_{0.05}$Al${}_{0.05}$O${}_2$ cathode obtained by a conventional co-precipitation method that has a uniform Al distribution throughout the bulk (B-NCA). The S-NCA cathode greatly outperform with an impressive capacity retention of 84% after 1000 cycles in pouch full cells with graphite anode compared to 62% retention for B-NCA. Advanced surface characterization methodologies, including time-of-flight secondary-ion mass spectrometry, reveal that the Al-enriched surface morphology facilitates the formation of a robust, thin electrode-electrolyte interphase (EEI), effectively suppressing the oxidative decomposition of the electrolyte, gas generation, and metallic dead lithium formation on graphite anode. The results illustrate that surface reactivity with the electrolyte is the primary factor limiting the cycle of cells with high-Ni cathodes. The work provides valuable insights toward the practical viability of ultrahigh-Ni cathodes in lithium-ion batteries. (© 2023 Wiley‐VCH GmbH)