Abstract The interface between the electrocatalyst and electrolyte is critical in seawater electrolysis for hydrogen production, yet optimizing interfacial H‐bond for enhanced catalytic activity and stability remains a significant challenge. This work demonstrates surface Lewis base (LB)‐mediated reconstruction of interfacial water H‐bond network within the electrochemical double layer toward enhanced seawater oxidation. The LB silicate species can be effectively immobilized on the surface of Ni(OH) 2 by electrochemical activation. In situ spectroscopy experiments show the LB‐induced reconstruction of the H‐bond network facilitates rapid OH − enrichment, reduces local acidity, and prevents surface Cl − corrosion on Ni(OH) 2 , significantly improving seawater oxidation activity and long‐term stability. Theoretical calculation further elucidates the key mechanism of the highly wettable silicate layers that can preferentially adsorb OH − while resisting Cl − . The optimized Ni(OH) 2 ‐Silicate achieves 121 mV reduction in overpotential at 200 mA cm −2 , stable operation for 620 h at industrial 1 A cm −2 , and robust activity for over 270 h at 1 A cm −2 in alkaline anion‐exchange membrane seawater electrolyzer. This LB‐induced strategy paves an avenue of regulating the interfacial microenvironment for durable chloride‐resisting electrocatalysis.