A general method to heterogenize, stabilize and significantly enhance the activity of selective visible light photocatalysts for aerobic oxidation of glycerol is devised. The new method makes use of the sol–gel encapsulation of photocatalytic species in silica-based matrices to afford leach-proof catalysts capable to afford valued products at low cost with little or no waste generation. In particular, the photocatalytic selective conversion of glycerol is performed in water solvent under ambient conditions with molecular oxygen as oxidant and visible light as the driving energy source, thereby meeting all requirements for a green chemical process. Entrapment of the semiconductor-based photocatalyst inside the transparent porous silica matrix enhances substrate adsorption, thus improving its local concentration and favoring reaction with the photogenerated active species.