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Ni-rich cathodes stand out for their ability to achieve high energy density in Li-ion batteries. However, their long-term cycling stability is challenged by excessive oxygen redox activity, the fundamental atomic-scale behavior of which remains poorly understood—particularly the nature of oxygen double ligand hole states and their suppression. This study demonstrates that Jahn–Teller distortion promotes unexpected intralayer O─O pairing, coupled with Ni─O hybridization, leading to the formation of double ligand holes in LiNiO2 and oxygen evolution at high state-of-charge (SoC). These intralayer O─O pairs are visualized by 4D scanning transmission electron microscopy and identified as peroxo-like species with an average O─O distance of 2.428 Å at 60% SoC. Meanwhile, substitution with elements such as Al3+ and Sc3+, which possess low electronegativity and an np6 electron configuration, induces an abnormal inductive effect that deviates from conventional electronegativity-based frameworks. This phenomenon is attributed to electron localization on lattice oxygen, which effectively prevents local lattice distortion and the accumulation of TM─O and O─O ligand holes. These findings establish a fundamental correlation between structural deformation and ligand hole states, advancing the conceptual framework for Ni-rich cathode design beyond conventional molecular orbital theory and electronegativity-guided substitution strategies.