Li-rich layered oxide cathode materials show high capacities in lithium-ion batteries owing to the contribution of the oxygen redox reaction. However, structural accommodation of this reaction usually results in O–O dimerization, leading to oxygen release and poor electrochemical performance. In this study, we propose a new structural response mechanism inhibiting O–O dimerization for the oxygen redox reaction by tuning the local symmetry around the oxygen ions. Compared with regular Li2RuO3, the structural response of the as-prepared local-symmetry-tuned Li2RuO3 to the oxygen redox reaction involves the telescopic O–Ru–O configuration rather than O–O dimerization, which inhibits oxygen release, enabling significantly enhanced cycling stability and negligible voltage decay. This discovery of the new structural response mechanism for the oxygen redox reaction will provide a new scope for the strategy of enhancing the anionic redox stability, paving unexplored pathways toward further development of high capacity Li-rich layered oxides.

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