Translating Molecular Order Into Interfacial Function: Sodium Nucleation and Interphase Evolution Regulation for Ultra‐Stable Anode‐Less Cycling

ABSTRACT Interfacial design remains a central challenge in enabling anode‐less sodium (Na) metal batteries, where stability, uniform plating, and SEI integrity must all emerge from a bare current collector. Here, we report a rational strategy to pre‐program the interphase through laser‐mediated translation of a crystalline covalent organic framework (COF) into a chemically, morphologically, and electronically optimized carbon scaffold. By selecting a porphyrin‐triazine‐based COF with extended conjugation, heteroatom functionality, and in‐plane order, we achieve a transformed C@COF surface that retains topological coherence and delivers spatially uniform sodiophilicity. Operando imaging coupled with voltammetry reveals stochastic and gas‐evolving growth on bare Cu, in contrast to smooth, synchronous Na deposition with minimal parasitic reactions on the C@COF interface. COMSOL simulations further capture how compositional and topological tuning redistributes electric field lines, flattens potential gradients, and minimizes nucleation overpotentials. This results in a high average Coulombic efficiency (∼99.4%) with exceptional stability of over 5000 cycles of reversible Na plating‐stripping and robust rate capability up to 10 mA cm −2 , ultimately achieving long‐cycling anode‐less C@COF||NVP full cells. By translating molecular architecture into interfacial function, this strategy offers a blueprint for designing kinetically intelligent and chemically adaptive interfaces, opening new directions for programmed surface engineering in metal‐anode battery systems.