The ethanol surface reaction over CeO₂ nanooctahedra (NO) and nanocubes (NC), which mainly expose (111) and (100) surfaces, respectively, was studied by means of infrared spectroscopy (TPSR-IR), mass spectrometry (TPSR-MS) and density functional theory (DFT) calculations. TPSR-MS results show that the production of H₂ is 2.4 times higher on CeO₂ -NC than on -NO, which is rationalized starting from the different types of adsorbed ethoxy species controlled by the shape of the ceria particles. Over the CeO₂(111) surface, monodentate type I and II ethoxy species with the alkyl chain perpendicular or parallel to the surface, respectively, were identified. Whereas on the CeO₂(100) surface, bidentate and monodentate type III ethoxy species on the checkerboard O-terminated and on a pyramid of the reconstructed (100) surface, respectively, are found. The more labile surface ethoxy species on each ceria nanoshape, which are the monodentate type I or III ethoxy on CeO₂ -NO and -NC, respectively, react on the surface to give acetate species that decomposes to CO₂ and CH₄, while H₂ is formed via the recombination of hydroxyl species. In addition, the more stable monodentate type II and bidentate ethoxy species on CeO₂ -NO and -NC, respectively, give an ethylenedioxy intermediate the binding of which is facet dependent. On the (111) facet, the less strongly bound ethylenedioxy desorbs as ethylene, whereas on the (100) facet, the more strongly bound intermediate also produces CO₂ and H₂ via formate species. Thus, on the (100) facet an additional pathway towards H₂ formation is found. ESR activity measurements show an enhanced H₂ production on the nanocubes.