Lithium-rich layered oxides (LLOs) are considered promising cathode candidates for high-energy-density lithium-ion batteries. However, poor cycle stability and limited rate performance severely hinder their practical application. Herein, the strong Nb_4d-O_2p configurations at the Mn sites regulating the p-band center of the O 2p are designed to inhibit oxygen release and relieve cycle degradation. Meanwhile, the in situ constructed Li₃PO₄ surface coating is presented to obtain an excellent transmission rate of Li⁺. Consequently, LLO-NP exhibits excellent performance, delivering a capacity retention of 83.6% at 45 °C after 200 cycles (compared to 61.5% for the unmodified LLO), and a rate capability of 199 mAh g⁻¹ at 3 C (compared to 174.8 mAh g⁻¹ for the unmodified LLO). Integrating oxygen coordination regulation with surface structure design, this novel modification strategy inspires the design of high-performance LLOs.