Hierarchical VO ₂ @BiVO ₄ Films Decorated With Porous BiVO ₄ Nanoplates for Durable and Self‐Cleaning Smart Windows

VO 2 is a promising thermochromic material, but it is still limited by low transparency, weak solar modulation, and poor stability. Here, we develop a coordination‐compound‐derived strategy to construct a hierarchical BiVO 4 /VO 2 @BiVO 4 film with a core–shell@nanosheet structure. VO 2 @BiVO 4 nanoparticles form the inner layer, whereas porous BiVO 4 nanosheets assemble on the surface. This architecture provides synergistic benefits: The BiVO 4 shell protects VO 2 from oxidation and enhances plasmon‐induced solar modulation, and the nanosheets improve visible transparency via antireflection. The composite also exhibits photocatalytic self‐cleaning and antibacterial activity. It delivers 63.0% visible transmittance and 15.6% solar modulation, retaining 80% performance after 27 days at 100°C and 50% humidity. This work integrates optical performance, durability, and multifunctionality, offering a practical pathway for VO 2 ‐based smart windows.