Valorization of glycerol into high added-value products by photocatalysis can not only create good economic benefits, but also cater to the global low-carbon and energy-saving environmental protection needs. In this study we proposed, for the very first time, to perform the photooxidation of glycerol towards added-value products with homemade WO3 and commercial WO3/TiO2 (DTW5)). Their performance was compared with that of state-of-the-art TiO2-based photocatalysts (Anatase, Rutile, and P25). We found that, while TiO2 favours the total oxidation of glycerol, WO3-based materials exhibit an outstanding selectivity towards one of the most valuable oxidation products: glyceraldehyde. It was attributed to their enhanced acidity, which selectively activates CO bonds in glycerol and facilitates the further desorption of glyceraldehyde to the liquid phase. This study establishes therefore a new starting point towards the development of advanced materials for an efficient valorization of glycerol.