Oxygen-redox-based-layered cathode materials are of great importance in realizing high-energy-density sodium-ion batteries (SIBs) that can satisfy the
demands of next-generation energy storage technologies. However, Mn-basedlayered materials (P2-type Na-poor Nay[AxMn1-x]O2  where A = alkali ions) still suffer from poor reversibility during oxygen-redox reactions and low conductivity.
In this work, the dual Li and Co replacement is investigated in P2-type-layered NaxMnO2. Experimentally and theoretically, it is demonstrated that the efficacy of the dual Li and Co replacement in Na0.6[Li0.15Co0.15Mn0.7]O2 is that it improves
the structural and cycling stability despite the reversible Li migration from the transition metal layer during de-/sodiation. Operando X-ray diffraction and ex situ neutron diffraction analysis prove that the material maintains a P2-type structure during the entire range of Na+ extraction and insertion with a small volume change of ≈4.3%. In Na0.6[Li0.15Co0.15Mn0.7]O2, the reversible electrochemical activity of Co3+/Co4+, Mn3+/Mn4+, and O2-/(O2)n- redox is identified as a reliable mechanism for the remarkable stable electrochemical performance. From a broader perspective, this work highlights a possible design roadmap for developing cathode materials with optimized cationic and anionic activities and excellent structural stabilities for SIBs.