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Increasing the charging cut‐off voltage (e.g., 4.6 V) to extract more Li ions are pushing the LiCoO2 (LCO) cathode to achieve a higher energy density. However, an inhomogeneous cycled bulk‐to‐surface Li distribution, which is closely associated with the enhanced extracted Li ions, is usually ignored, and severely restricts the design of long lifespan high voltage LCO. Here, a strategy by constructing an artificial solid–solid Li diffusion environment on LCO's surface is proposed to achieve a homogeneous bulk‐to‐surface Li distribution upon cycling. The diffusion optimized LCO not only shows a highly reversible capacity of 212 mA h g−1 but also an ultrahigh capacity retention of 80% over 600 cycles at 4.6 V. Combined in situ X‐ray diffraction measurements and stress‐evolution simulation analysis, it is revealed that the superior 4.6 V long‐cycled stability is ascribed to a reduced structure stress leaded by the homogeneous bulk‐to‐surface Li diffusion. This work broadens approaches for the design of highly stable layered oxide cathodes with low ion‐storage structure stress. [ABSTRACT FROM AUTHOR]