PtSn/CeO2–C electrocatalysts were prepared by an alcohol-reduction process using ethylene glycol as solvent and reduction agent and CeO2 and Vulcan Carbon XC72 as supports. The electrocatalysts were characterized by EDX and XRD. The electro-oxidation of ethanol was studied at room temperature by chronoamperometry. PtSn/CeO2–C electrocatalyst with 15 wt% of CeO2 showed a significant increase of performance for ethanol oxidation compared to PtSn/C catalyst. Preliminary tests at 100 °C on a single cell of a direct ethanol fuel cell (DEFC) also confirm the results obtained by chronoamperometry.