Engineering Vanadium Oxide Coordination Structure and Exposing Specific Crystal Planes for High‐Performance Electrochromism

ABSTRACT The electrochromic performance of vanadium pentoxide is limited by sluggish ion diffusion kinetics and poor cycling stability. Herein, we present an effective strategy to regulate the V─O chemical coordination environment and preferentially expose the (001) crystal planes, thereby enabling rapid Zn‐ion diffusion, faster switching kinetics, and enhanced long‐term stability. Impressively, in situ testing and density functional theory reveal that the synergy between the [VO ₆ ] octahedra and exposed (001) facets enhances electrochromic performance by enabling efficient ion diffusion pathways, providing ample storage sites, and facilitating charge transfer. The resulting thin films exhibit rich, reversible color transitions spanning from orange‐red to blue‐gray, along with a high optical modulation of 59.4% at 668 nm. Furthermore, the electrochromic films are adaptable to diverse natural environments, enabling applications in adaptive camouflage and visual monitoring of energy states via color conversion. This work provides fundamental insights into structure‐property relationships in V ₂ O ₅ and offers a rational design strategy for high‐performance electrochromic materials in next‐generation smart devices.