ABSTRACT Direct seawater electrolysis is severely constrained by the activity‐durability trade‐off and chloride‐induced corrosion. Herein, we design corrosion‐resistant, highly selective layered double hydroxide (LDH) catalysts by transitioning interlayer bonding from weak electrostatic attraction to strong coordination. Amphiphilic dodecylbenzenesulfonate (SDBS) coordinates with Fe active centers, forming robust Fe─O─S bonds that establish a securely locked microenvironment. Density functional