Abstract Silica spheres coated with titania (SiO2@TiO2) were synthesized using chitosan as template. The N2 adsorption/desorption isotherms of the spheres point to meso and macroporous characteristics and the elemental mapping by EDS shows uniform distribution of Ti on the surface of the silica spheres, leading to formation of an amorphous structure (XRD). The results from the model reaction of photocatalytic degradation of methylene blue (MB) show a good stability of the spheres regarding their reuse. The tests with various additives pointed to hydroxyl radical production as the main via of MB degradation. The photocatalytic activity of the spheres in the hydroxylation of benzene to form phenol, hydroquinone and benzoquinone was assessed. The kinetic data point to the formation of phenol as the limiting step; in addition, the phenol consumption occurs by parallel and consecutive reactions producing benzoquinone.