TiO2/WO3 composites are widely in the literature as engineered systems for photocatalytic and (photo) electrochemical applications, since the presence of WO3 can promote both visible light absorption and electron transfer phenomena of TiO2. The preparation of these system, depending on the preparation method, can also affect the surface feature with respect to TiO2, modifying adsorption and performance, as well as the reaction mechanisms. Here, TiO2/WO3 composites were prepared by precipitation of WO3 onto the TiO2 surface and characterized in terms of their structural, morphological, optical and surface properties. Raman and IR spectroscopy as well as a marked shift in the isoelectric point support the preferential surface location of WO3. Samples were photocatalytically tested towards the degradation of ethanol and of tetracycline and the adsorption and degradation behaviour were studied, suggesting, in both cases, significant variations of the reaction paths by the addition of WO3.