Frustrated Lewis Pair Mediated f‐p‐d Orbital Coupling: Achieving Selective Seawater Oxidation and Breaking *OH and *OOH Scaling Relationship

The development of materials for hydrogen production via seawater electrolysis at high current densities plays a crucial role in producing renewable hydrogen energy. However, during the seawater electrolysis process, the anode inevitably undergoes chloride oxidation reaction (ClOR) due to Cl‐ adsorption, making the seawater electrolysis process difficult to sustain. Inspired by the selective permeability of cell membranes, we propose a biomimetic design of frustrated Lewis pairs (FLPs) layers. Combining experimental results and molecular dynamics simulations, it has been demonstrated that cerium dioxide layers with FLPs sites can decompose water molecules, capture hydroxyl anions, and repel chloride ions simultaneously. DFT theoretical analysis indicates that the FLP sites regulate the Ce 4f‐O 2p‐Ni 3d gradient orbital coupling, providing additional oxygen non‐bonding (ONB) to stabilize the Ni‐O bond and optimize the adsorption strength of intermediates, thereby breaking the *OH and *OOH scaling relationship. Assembled anion exchange membrane electrolyzers exhibit an efficiency of 95.7% at a current density of 0.1 A cm‐2 and can stably operate for 250 hours at a current density of 0.2 A cm‐2.