<p>Deposition aspects, photoelectrochemical (PEC) properties and performance for water oxidation of anisotropically crystallized monoclinic WO₃ films with the preferential (202) plane were investigated. The pre-coating of a seed layer on the fluorine-doped tin oxide (FTO) electrodes turned out to be necessary for the deposition of the anisotropic WO₃ films by a hydrothermal method. The anisotropic WO₃ (denoted as WO₃(MS) and WO₃(PS), respectively) films were deposited on the FTO surface coated by two different seed layers which were formed by a mixed metal-imidazole casting (MiMIC) method (MiMIC-seed layer) and common method using peroxo-tungstic acid (PA) (PA-seed layer). The incident photon to electron conversion efficiency (IPCE₄₂₀) of 38% at 420&#xa0;nm for WO₃(MS) was 1.2 times higher than that (31%) for the WO₃(PS) electrode, although the morphological properties and thickness of both the films were hardly influenced by the seed layers. The PEC stability for water oxidation (95% photocurrent retention and Faraday efficiency (FE) of 95%) for the WO₃(MS) electrode was also higher than that (90% photocurrent retention and FE of 88%) for the WO₃(PS) electrode. Photoelectrochemical impedance spectroscopic (PEIS) measurement suggested the effective electron transfer from the bulk WO₃ film to the FTO electrode through the MiMIC-seed layer which has a flawless and smooth layer with less-particle morphology, compared to the PA-seed layer with granular morphology composed of relatively larger particles. The effective electron transfer through the MiMIC-seed layer is responsible for the higher IPCE and PEC stability for the WO₃(MS) electrode compared to those of the WO₃(PS) electrode.</p>