Selective photocatalytic oxidation of benzyl alcohol to benzaldehyde and reduction of nitrobenzene to aniline reactions are investigated by using SiO2@TiO2 spheres produced in a simple route using chitosan as a template. The spheres are predominantly macroporous and, the XRD points out an amorphous crystallographic profile suggesting the uniform distribution of TiO2. Under low-power lighting for 4 hours, the conversions achieved was of the order of 49% and 99% for benzyl alcohol and nitrobenzene, respectively, with selectivity to benzaldehyde and aniline of 99% in both reactions. The study also follows the effects of the solvent and the presence of O2.