Nanoparticles of gold on TiO2 are highly chemoselective for the reduction of substituted nitroaromatics, such as nitrostyrene. By combining kinetics and in situ IR spectroscopy, it has been found that there is a preferential adsorption of the reactant on the catalyst through the nitro group. IR studies of nitrobenzene, styrene, and nitrostyrene adsorption, together with quantum chemical calculations, show that the nitro and the olefinic groups adsorb weakly on the Au(111) and Au(001) surfaces, and that although a stronger adsorption occurs on low-coordinated atoms in gold nanoparticles, this adsorption is not selective. On the other hand, an energetically and geometrically favored adsorption through the nitro group occurs on the TiO2 support and in the interface between the gold nanoparticle and the TiO2 support. Such preferential adsorption is not observed with nanoparticles of gold on silica which, contrary to the Au/TiO2 catalyst, is not chemoselective for the reduction of substituted nitroaromatic compounds. Therefore, the high chemoselectiviy of the Au/TiO2 catalyst can be attributed to a cooperation between the gold nanoparticle and the support that preferentially activates the nitro group.