CeO2 microspheres and nanotubes were synthesized via the hydrothermal route. Catalytic properties of the Pd/CeO2 catalysts were investigated using the low-concentration methane oxidation as probe reaction. The structures and morphologies were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Nitrogen ad/desorption, X-ray photoelectron spectroscopy, and Raman techniques. The results show that the catalytic activity is strongly dependent on the morphology of CeO2. The property of Pd/CeO2-microspheres catalyst is superior to that of Pd/CeO2-nanotubes, which is attributed to its short porous channel, the exposed active planes, and existence of CeO2-x . The Pd/CeO2-microspheres catalyst will be a promising candidate for low-concentration methane oxidation.