Ligand‐Engineered <i>p</i> ‐Orbital Occupancy Modulation Activates Lattice Oxygen for Efficient and Selective Urea Electrooxidation

ABSTRACT Electrochemical urea oxidation reaction (UOR) offers a promising alternative to oxygen evolution reaction (OER) in water electrolysis, enabling simultaneous energy‐efficient hydrogen production and urea‐rich wastewater remediation. However, sluggish kinetics and the inevitable competition from OER, especially at high anodic potentials, continue to impede its practical application. Herein, we report a ligand‐engineered NiFe layered double hydroxide intercalated with trifluoroacetate (CF 3 COO – ), termed CF 3 ‐LDH, to address these limitations. Leveraging the strong electron‐withdrawing nature of the –CF 3 group, CF 3 COO – drives electron transfer from Ni and Fe centers to the ligand, thereby lowering the local electron density, stabilizing high‐valent Ni (2+δ)+ and Fe (3+α)+ species, and unlocking the reactivity of adjacent lattice oxygen sites. In situ spectroscopic analyses reveal that CF 3 COO – intercalation suppresses NiOOH formation and mitigates OH – oversaturation, thus attenuating the parasitic OER pathway and ensuring UOR selectivity. Theoretical calculations further confirm that the lattice oxygen sites with engineered p ‐orbital occupancy reduce the energy barriers of key UOR steps and optimize the adsorption of critical intermediates. As a result, CF 3 ‐LDH exhibits superior UOR activity, requiring only 1.32 V to reach 10 mA cm −2 with a Tafel slope of 29 mV dec −1 . When integrated into an anion exchange membrane (AEM) electrolyzer, the system delivers 100 mA cm −2 at just 1.36 V at 60°C and maintains stable operation over 200 h. This work highlights the efficacy of ligand‐directed lattice oxygen activation in promoting pathway‐selective UOR and presents a viable strategy for designing high‐performance anodes toward integrated clean hydrogen generation and wastewater treatment.