In recent years, nanoporous alloys have presented the advantages of a large specific surface area, low density, and simple operation, and they have been widely used in the fields of catalysis, magnetism, and medicine. Nanoporous Pt-Si alloy was prepared by melt-spun and chemical dealloying, and was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope, and transmission electron microscopy. Pt-Si alloys possess a three-dimensional bicontinuous structure and an average size of 5 nanometers. Compared with commercial Pt/C catalysts, nanoporous Pt-Si alloys exhibit excellent electrocatalytic activity and stability in ethanol-catalyzed oxidation reactions. It is taken into consideration to be a promising catalyst in direct ethanol fuel cells.