Pt on mesostructured CeO2 nanoparticles embedded within ultrathin layers of highly structured SiO2 binder shows highest activity reported with 80% selectivity for the chemoselective hydrogenation of crotonaldehyde. Characterization by transmission electron microscopy (TEM), CO adsorption, and X-ray photoelectron spectroscopy (XPS) show the presence of small Pt metal particles, preferentially located on CeO2 (70%) together with the formation of Pt-CeO2-x, sites at the interface between Pt and CeO2 (4 nm) nanoparticles. These sites are able to polarize the carbonyl group and facilitate the selective hydrogenation of this with respect to the double bond.