Hydrogen production for fuel cells from ethanol partial oxidation was evaluated on 1% Rh/CeO2 catalyst. Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) were used to analyze carbon formation and the possible sintering of the metallic phase. X-ray fluorescence (XRF), nitrogen adsorption, and temperature-programmed reduction (TPR) were also used for catalyst characterization. Two groups of rhodium particles of different sizes were observed. By SEM/EDS analysis, no residual chloride was identified. TEM made it possible to identify the presence of rhodium in small clusters. On the other hand, products distribution was affected by reaction temperature. At 473 K, only traces of acetaldehyde were detected for the Rh/CeO2 catalyst. In the reaction conditions, no deactivation of the catalyst due to carbon deposition or sintering of the metal was observed. Overall, our results show that the performance of Rh/CeO2 catalyst points to promising applications in terms of H-2 production for fuel cells technology by ethanol partial oxidation.