Monoclinic n-type bismuth vanadate (BiVO₄) has emerged as a benchmark photoanode material for solar-driven photoelectrochemical (PEC) water splitting due to its ideal band alignment with water redox potentials, ease of synthesis, and high charge extraction efficiency. Despite these advantages, BiVO₄ suffers from several intrinsic limitations such as a relatively wide band gap, low electronic conductivity, and high recombination rates that hinder its practical PEC performance. Addressing these challenges requires a fundamental understanding of how to engineer the material’s electronic and optical properties—especially through doping and defect manipulation. This research investigates the effects of non-metal doping and intrinsic vacancies, paving the way for performance-optimized BiVO₄ photoanodes. Electronic Structure Tuning through Nitrogen Doping The substitution of nitrogen into the BiVO₄ lattice significantly alters its electronic structure, leading to a reduction in band ...