WO 3 thin films have been deposited onto glass and FTO coated glass substrates using simple chemical spray pyrolysis technique. The effect of solution concentration on the photoelectrochemical (PEC), structural, morphological and photoelectrocatalytic properties has been investigated. The structure and morphology of WO 3 photoelectrodes are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The PEC study shows that both open circuit voltage (V oc ) and short circuit current (I sc ) at the optimized solution concentration (0.125 M) are relatively maximum (I sc = 0.62 mA and V oc = 0.58 V). XRD study reveals that the films are polycrystalline in nature with monoclinic crystal structure. SEM images show that the substrate surface is well covered with uniform, compact and fine grain like morphology. The AFM image shows the rough nature of the film. Photoelectrocatalytic degradation of methyl red dye in aqueous solutions is studied. The end result shows that the degradation percentage of methyl red using WO 3 photoelectrode has reached 97 % under visible light illumination after 160 min. The amount of mineralization is confirmed by COD and TOC analysis.