A new silicon-based anode suitable for direct ethanol fuel cells (DEFCs) is described. Pd–Ni nanoparticles are coated on Si nanowires (SiNWs) by electroless co-plating to form the catalytic materials. The electrocatalytic properties of the SiNWs and ethanol oxidation on the Pd–Ni catalyst (Pd–Ni/SiNWs) are investigated electrochemically. The effects of temperature and working potential limit in the anodic direction on ethanol oxidation are studied by cyclic voltammetry. The Pd–Ni/SiNWs electrode exhibits higher electrocatalytic activity and better long-term stability in an alkaline solution. It also yields a larger current density and negative onset potential thus boding well for its application to fuel cells.