Customizing Electronic‐Physical Dual‐Shield Interlayers via d‐p Orbital Hybridization for Ultra‐Stable Zinc Metal Anodes

Metal–organic frameworks (MOFs) are promising protective interlayers to mitigate Zn dendrite growth and parasitic side reactions, yet their aqueous vulnerability and unresolved electronic mechanisms hamper practical application. Herein, we propose an electronic structure engineering strategy via d‐p orbital hybridization to customize the Zn anode interphase. Using UiO‐66 derivatives (‐NH 2 , ‐COOH, and ‐F 4 ) as models, theoretical calculations reveal that strengthening the substituents’ electron‐withdrawing capability deepens d‐p orbital coupling and shifts the π* d‐band center toward the Fermi level, thus inducing intense spatial charge polarization and enhancing Zn 2+ affinity. Experimentally, the highly fluorinated UiO‐66‐F 4 achieves the highest Zn 2+ adsorption, drives selective SO 4 2− exclusion, accelerates desolvation, and enables rapid ion transport. Synergizing with inherent physical hydrophobicity, this unique electronic‐physical dual‐shield of the UiO‐66‐F 4 interlayer effectively averts H 2 O‐induced side reactions and ensures highly reversible Zn plating/stripping. Consequently, the Zn@UiO‐66‐F 4 anode delivers a 3600 h lifespan at 5 mA cm −2 and sustains 560 h under a stringent 90% depth of discharge, outperforming most MOF‐modified anodes. Furthermore, flexible full cells exhibit impressive cycling stability and reliably power wearable systems even under severe deformation. Overall, this work establishes d‐p orbital hybridization regulation as a powerful paradigm for customizing advanced functional interlayers toward ultra‐stable Zn metal anodes.