Although anodic tungsten oxide has attracted increasing attention in recent years, there is still a lack of detailed studies on the photoelectrochemical (PEC) properties of such kind of materials grown in different electrolytes under various sets of conditions. In addition, the morphology of photoanode is not a single factor responsible for its PEC performance. Therefore, the attempt was to correlate different anodizing conditions (especially electrolyte composition) with the surface morphology, oxide thickness, semiconducting, and photoelectrochemical properties of anodized oxide layers. As expected, the surface morphology of WO3 depends strongly on anodizing conditions. Annealing of as-synthesized tungsten oxide layers at 500 °C for 2 h leads to obtaining a monoclinic WO3 phase in all cases. From the Mott-Schottky analysis, it has been confirmed that all as prepared anodic oxide samples are n-type semiconductors. Band gap energy values estimated from incident photon−to−current efficiency (IPCE) measurements neither differ significantly for as−synthesized WO3 layers nor depend on anodizing conditions such as electrolyte composition, time and applied potential. Although the estimated band gaps are similar, photoelectrochemical properties are different because of many different reasons, including the layer morphology (homogeneity, porosity, pore size, active surface area), oxide layer thickness, and semiconducting properties of the material, which depend on the electrolyte composition used for anodization.