Epitaxial Substrate Engineering Enables Ultrastable Zinc Anodes via Low‐Lattice‐Mismatch Interface‐Induced Dendrite Regulation

Aqueous zinc‐ion batteries (AZIBs) have gained considerable interest as next‐generation energy storage systems owing to their intrinsic safety, economic advantages, and competitive theoretical capacity. However, two persistent challenges at the zinc anode interface—uncontrolled dendritic crystallization and water‐induced parasitic reactions—severely compromise their cyclability. Here, a stable multifunctional ZTO (ZnTiO 3 ) insulating coating is designed and constructed on Zn anode, which can effectively inhibit the dendrites formation and zinc anode corrosion. Through combined experimental analysis and density functional theory simulations, it is revealed that the high matching between ZTO and Zn(002) enables the formation of a stable interface between Zn and ZTO during repeated charge‐discharge processes. This coherent interface regulates zinc‐ion flux distribution, inducing preferentially oriented deposition along the (002) plane while maintaining ionic transport continuity. In addition, ZTO mitigates the water‐related side reactions by repelling/adsorbing H from reactive H 2 O through Zn/O sites. The optimized Zn‐ZTO configuration demonstrates exceptional durability in symmetric cells, achieving unprecedented cycling stability exceeding 8,800 h at 1 mA cm −2 /1 mAh cm −2 . This study expands the protective layer screening strategy, improves the understanding of the plating/stripping mechanism of Zn 2+ , and lays the foundation for further development of stable Zn‐metal batteries.