Multiple‐Center Cation Ordering Mitigates Voltage Decay and Hysteresis in Sodium Layered Oxides

P2‐type layered oxides, as promising cathode candidates for sodium‐ion batteries (SIBs), offer high working voltage and rapid Na + transport, yet suffer from progressive voltage decay and structural instability at deep states of charge, due to detrimental P2‐O2 phase transitions and irreversible oxygen redox. Herein, we introduce a multiple‐center honeycomb ordering strategy that incorporates LiMn 6 , MgMn 6, and intrinsic NiMn 6 topology within the transition‐metal layers of P2‐Na 0.67 Ni 0.33 Mn 0.67 O 2 through rational Li/Mg co‐doping. We demonstrate that the LiMn 6 order units disperse the NiMn 6 superstructure domains to suppress long‐range phase evolution, while the MgMn 6 motifs act as nanoscale anchors to immobilize Li + within the TM slabs and prevent its migration during oxygen redox. This synergistic topological design sustains a highly reversible solid‐solution reaction over a wide voltage range of 2.0–4.5 V, with minimal voltage hysteresis and a voltage decay of 0.002 V per cycle. The resulting P2‐Na 0.76 Li 0.10 Mg 0.08 Ni 0.15 Mn 0.67 O 2 cathode delivers a high capcity of 134 mAh g −1 and retains an excellent capacity retention of 93.36% after 400 cycles, outperforming conventional analogues. These findings open a new avenue for tailoring the local structure of layered oxide cathodes to achieve voltage‐stable and high‐energy‐density SIBs.