Oriented Zn Deposition for Stable Anodes via Long‐Chain Molecular Interfacial Engineering

Uncontrolled dendrite growth and parasitic reactions severely degrade Zn anodes. To address this, we introduce a long‐chain molecular additive that orchestrates interfacial engineering at the electrode–electrolyte interface. The molecule enables biased adsorption on Zn surfaces, tailors the solvation sheath, and contributes to a ZnS‐containing organic/inorganic SEI. This coupled adsorption–SEI regulation promotes early‐stage Zn(002)‐preferred deposition and subsequently stabilizes Zn 2+ transport, thereby suppressing dendrites and side reactions. This synergistic regulation achieves highly oriented Zn deposition, significantly suppressing dendrites and hydrogen evolution. Consequently, the symmetric cell delivers exceptional cycling stability exceeding 2900 h at 1.0 mA cm −2 and 1.0 mAh cm −2 , and an average Coulombic efficiency of 99.81% over 3500 cycles in asymmetric cells. High‐loading Zn||NH 4 V 4 O 10 full cell (DOD Zn ≈ 25%) exhibits a capacity retention rate exceeding 94% for 1000 stable cycles at 1 A g −1 . This work provides a fundamental insight into molecular design principles for regulating metal electrodeposition behavior.