Composite WO3/TiO2 nanostructures with optimal properties that enhance solar photoconversion reactions were developed, characterized, and tested. The TiO2 nanotubes were prepared by anodization of Ti foil and used as substrates for WO3 electrodeposition. The WO3 electrodeposition parameters were controlled to develop unique WO3 nanostructures with enhanced photoelectrochemical properties. Scanning electron microscopy (SEM) images showed that the nanomaterials with optimal photocurrent density have the same ordered structure as TiO2 nanotubes, with an external tubular nanostructured WO3 layer. Diffuse reflectance spectra showed an increase in the visible absorption relative to bare TiO2 nanotubes and in the UV absorption relative to bare WO3 films. Incident simulated solar photon-to-current efficiency (IPCE) increased from 30% (for bare WO3) to 50% (for tubular WO3/TiO2 composites). With the addition of diverse organic pollutants, the photocurrent densities exhibited more than a 5-fold increase. Chemical oxygen demand measurements showed the simultaneous photodegradation of organic pollutants. The results of this work showed that the unique structure and composition of these composite WO3/TiO2 materials enhance the IPCE efficiencies, optical properties, and photodegradation performance compared with the parent materials.