We report a facile method for the synthesis of Pd nanostructures with highly open structure and huge surface area by reducing Na2PdCl4 with ascorbic acid and using cetylpyridinium chloride (CPC) as a surfactant in an aqueous solution. The prepared Pd nanostructures had an average overall size of 70 nm and were composed of dozens of needle-like thin arms, originating from the same core, with an average thickness of 2.3 nm; the arms looked like chestnut-burs. Time evolution of Pd nanostructures implied that small Pd particles generated at the early stage of the reaction by fast reduction grew via the particle attachment growth mechanism. The morphology and size of the Pd nanostructures could be readily controlled by varying the concentration of CPC; depending on the amount of CPC, the reduction rates varied the morphology of the Pd nanostructures. Because of the huge surface area and possible catalytically active sites, the prepared chestnut-bur-like Pd nanostructures exhibited greater electrocatalytic activity toward ethanol electrooxidation compared to other Pd nanocatalysts, including cubic and octahedral Pd nanocrystals, and even commercial Pd/C.