Ethanol steam reforming is one of the most promising ways to produce hydrogen from biomass, and the goal of this research is to investigate robust, selective and active catalysts for this reaction. In particular, this work is focused on the effect of the different ceria support preparation methods on the Ni active phase stabilization. Two synthetic approaches were evaluated: precipitation (with urea) and microemulsion. The effects of lanthanum doping were investigated too. All catalysts were characterized using N2-physisorption, temperature programmed reduction (TPR), XRD and SEM, to understand the influence of the synthetic approach on the morphological and structural features and their relationship with catalytic properties. Two synthesis methods gave strongly different features. Catalysts prepared by precipitation showed higher reducibility (which involves higher oxygen mobility) and a more homogeneous Ni particle size distribution. Catalytic tests (at 500 °C for 5 h using severe Gas Hourly Space Velocity conditions) revealed also different behaviors. Though the initial conversion (near complete) and H2 yield (60%, i.e., 3.6 mol H2/mol ethanol) were the same, the catalyst prepared by microemulsion was deactivated much faster. Similar trends were found for La-promoted supports. Catalyst deactivation was mainly related to coke deposition as was shown by SEM of the used samples. Higher reducibility of the catalysts prepared by the precipitation method led to a decrease in coke deposition rate by facilitating the removal of coke precursors, which made them the more stable catalysts of the reaction.