One-step selective hydrogenation of nitroaromatics to obtain symmetric azocompounds with high yields has been performed with a gold supported on cerium oxide catalysts. Au/TiO2 and Au/CeO2 catalysts direct the reaction by two different pathways and with different selectivities. In situ FTIR studies reveal that the surface concentration of the intermediate nitrosobenzene is decisive in directing the reaction trough the different reaction pathways. In this way, while on Au/TiO2 a fast hydrogenation of the nitrosobenzene intermediate leads to a low surface concentration of the nitrosocompound, on Au/CeO2 nitrosobenzene is more stabilized on the catalyst surface leading to a lower hydrogenation and a higher coupling rate, resulting in high selectivities to azobenzene. On Au/CeO2, the relative weak adsorption of the azo with respect to the azoxycompound on the catalyst surface avoids the consecutive hydrogenation of azocompounds to the corresponding anilines until all the azoxy has been consumed. Asymmetric azobenzenes have also been obtained with very high yields on TiO2, through the Mills reaction. (C) 2014 Elsevier Inc. All rights reserved.