Prussian blue compounds, [4] have been extensively explored. Among these candidates, P2-type layered transition metal (TM) oxides (Na x TMO 2 , 0.5 ≤ x ≤ 0.8) have attracted much attention because of their relatively high theoretical capacities and low costs. [5] Nevertheless, Na x TMO 2 materials usually undergo an undesired P2-O2 phase transition in high-voltage regions, leading to a large volume change, rapid capacity decay, and poor lifetime. [5b,6] Recently, this issue has been largely mitigated by doping inactive material elements (such as Li, [7] Mg, [6] Ti, [8] Al, [9] and Zn [10] ) in TM layers, but at the expense of specific capacity.Apart from the cationic redox, the utilization of anionic redox activities provides a new avenue for attaining high-capacity electrode materials. Nevertheless, the nature of the oxygen redox chemistry is still under active debate, and the representative hypotheses mainly include the following: i) Tarascon et al. visualized the formation of (OO) n− peroxo-like dimers with shortened OO distances in Li-rich layered electrode materials; [11] ii) Bruce et al. proposed that the localized electron holes on O atoms, rather than true O 2 2− peroxide, could be generated upon Li + removal; [12] while iii) Ceder et al. suggested that the nonbonding oxygen states from LiOLi structural configurations in alkalirich and disordered systems are responsible for the oxygen redox reaction. [13] More recently, the formation of molecular O 2 trapped Sodium-ion batteries (SIBs) have attracted widespread attention for large-scale energy storage, but one major drawback, i.e., the limited capacity of cathode materials, impedes their practical applications. Oxygen redox reactions in layered oxide cathodes are proven to contribute additionally high specific capacity, while such cathodes often suffer from irreversible structural transitions, causing serious capacity fading and voltage decay upon cycling, and the formation process of the oxidized oxygen species remains elusive. Herein, a series of Al-doped P2-type Na 0.6 Ni 0.3 Mn 0.7 O 2 cathode materials for SIBs are reported and the corresponding charge compensation mechanisms are investigated qualitatively and quantitatively. The combined analyses reveal that Al doping boosts the reversible oxygen redox reactions through the reductive coupling reactions between orphaned O 2p states in NaOAl local configurations and Ni 4+ ions, as directly evidenced by X-ray absorption fine structure results. Additionally, Al doping also induces an increased interlayer spacing and inhibits the unfavorable P2 to O2 phase transition upon desodiation/sodiation, which is common in P2-type Mn-based cathode materials, leading to the great improvement in capacity retention and rate capability. This work provides deeper insights into the development of structurally stable and high-capacity layered cathode materials for SIBs with anion-cation synergetic contributions.