Innovative support-free platinum (Pt) nanostructures were developed in this study for enhancing the anode catalyst activities and the power density of single cell for proton exchange membrane fuel cell (PEMFC) application. The platinum nanostructures were directly grown on carbon paper by a pulsed electrodeposition technique. The morphology of Pt nanostructures were investigated by SEM, and shown as dendritic structures instead of nanoparticles. A cyclic voltammetry analysis was carried out for characterizing the behavior of methanol oxidation on specimen bearing the Pt dendritic nanostructures in mixed 1 M methanol and 0.5 M sulfuric acid solutions. With its unique morphology, the Pt dendritic nanostructures could exhibit a good carbon monoxide tolerance and high efficiency without the joined Ruthenium (Ru) catalyst, which is very different from pure Pt nanoparticles. After the electrochemistry analysis, the single cell test was performed with our homemade dendritic Pt catalyst to understand the efficiency of the cell. Then we compared it with the commercial Pt-black catalyst at the same loading of the platinum catalyst.