BiVO ₄ ‐Based Photoanodes for Solar Fuel Production: From Bulk Doping to Multiphase Integrated Architectures

Bismuth vanadate (BiVO 4 ) is a promising photoanode for photoelectrochemical (PEC) solar fuel production owing to its visible‐light response and suitable band structure. However, its efficiency is still limited by poor charge mobility, severe bulk/surface recombination, and sluggish interfacial oxidation kinetics. Compared with recent reviews mainly focused on water oxidation or individual modification strategies, this review links defect chemistry, charge‐carrier dynamics, interfacial kinetics, operational stability, and coupled solar fuel production. Particular attention is given to vacancy engineering, advanced transient and in situ characterization, and the integration of BiVO 4 ‐based photoanodes into PEC CO 2 reduction and high‐value chemical synthesis systems. Finally, key challenges related to long‐term stability, scalable fabrication, and practical device integration are discussed, providing guidance for the design of efficient and durable BiVO 4 ‐based photoelectrodes.