• A one-step H3BO3 treatment introduces near-surface B doping and sodium borate interphase.
• Near-surface B doping reinforces the layered structure and suppresses irreversible oxygen redox.
• Sodium borate interphase ensures fast Na+ transport while mitigating electrolyte decomposition and TM dissolution.
• Optimized cathode exhibits superior electrochemical performance and exceptional air stability.
• Providing a practical pathway for achieving electrochemically robust and moisture-tolerant sodium-ion cathodes.
O3-type layered oxides are among the most promising cathode candidates for sodium-ion batteries, yet their practical use is constrained by irreversible oxygen redox at high voltages, parasitic side reactions, and pronounced moisture sensitivity. Here, we propose a one-step H3BO3 treatment that introduces an in-situ boride complex, enabling near-surface B doping and the formation of a conformal sodium borate interphase. The dual modification operates synergistically: B incorporation reinforces the layered framework and suppresses oxygen redox above 4.0 V, while the sodium borate layer, endowed with high Na+ conductivity, functions as a robust interfacial barrier. These effects collectively suppress transition-metal dissolution, mitigate electrolyte decomposition, and promote rapid Na+ transport. Benefiting from this design, the optimized cathode delivers 160.5 mAh g−1 at 0.1 C and retains 85.3 % capacity after 200 cycles at 1 C. Moreover, the sodium borate coating effectively blocks H+/H2O ingress, conferring exceptional air stability. After 150 cycles, 3-days-aged pristine cathode retains 4.7 % of the fresh capacity, whereas optimized cathode maintains nearly pristine cycling stability. Even after seven days of exposure, only trace Na2CO3 impurities are detected. This work establishes in situ boride complexes as a viable strategy to achieve electrochemically robust and moisture-tolerant sodium-ion cathodes for grid-scale energy storage.