Thin‐film bismuth vanadate, BiVO4 photoanode was fabricated on fluorine‐doped tin oxide via aerosol‐assisted chemical vapor deposition, AACVD, with ethylene glycol as a solvent. The structure and morphology of the BiVO4 thin film were analyzed using X‐ray diffraction and field emission scanning electron microscopy and found to have monoclinic clinobisvanite structure with a noncompact nanoparticle distribution. The optical properties and bandgap estimation showed the BiVO4 thin film exhibited a characteristic peak in the visible‐light region with bandgap energy of 2.43 eV. The photoelectrochemical properties were investigated in a 0.5 M Na2SO4 electrolyte without any sacrificial agent or electron/hole scavenger resulting in 0.73 mA cm−2 at 1.23 V vs. SCE. The electrochemical impedance spectroscopy revealed good charge‐transfer characteristics of the photoanode and the Mott–Schottky plot was used to estimate the conduction and valence‐band position of BiVO4.