Dynamic Asymmetry in O/N‐Coordinated Zn Single‐Atom Catalysts Promotes Sabatier‐Favorable Urea and Urea Peroxide Electrosynthesis

ABSTRACT Precise regulation of metal‒intermediate binding is essential for selective electrocatalysis, yet conventional symmetric single‐atom coordination often limits directional adsorption control. Here we report an asymmetric O/N‐co‐coordinated Zn single‐atom catalyst, Zn‐O 3 N 1 ‐C, using symmetric Zn‐O 4 ‐C as a structural counterpart. Structural characterization and x‐ray absorption spectroscopy (XAS) confirm atomically dispersed Zn‒O 3 N 1 sites, in which replacing one O ligand with less electronegative N not only breaks local symmetry, but also enriches Zn electron density and lowers the Zn oxidation state. Operando XAS further reveals that Zn–O 3 N 1 undergoes cathodic‐bias‐induced electronic enrichment and anisotropic Zn─N/Zn─O bond response, amplifying local coordination polarization while preserving the isolated Zn─O/N framework. This dynamically polarized asymmetric coordination shifts Zn‒adsorbate interactions toward a Sabatier‐favorable regime, enabling two adsorption‐governed transformations. For CO 2 /nitrate co‐reduction, Zn‐O 3 N 1 ‐C promotes *NO/*NHO‐mediated C‒N coupling. The same catalyst also demonstrates excellent electrocatalytic activity toward two‐electron oxygen reduction reaction (2e − ORR). The electrosynthesized urea and H 2 O 2 are further coupled to produce urea peroxide. Operando spectroscopy and density functional theory calculations reveal that asymmetric Zn–O 3 N 1 coordination optimizes *NO/*NHO and *OOH binding, establishing dynamic coordination polarization as a design principle for selective single‐atom electrocatalysis.