Carbonaceous sphere@MnO2 rattle-type hollow spheres were synthesized under mild experimental conditions. The as-prepared hollow structures were characterized using scanning electron microscope, transmission electron microscope, x-ray diffraction, x-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis, and nitrogen adsorption techniques. The characterization data showed the formation of rattle-type hollow structures with a mesoporous MnO2 shell and a carbonaceous sphere core. The composition and shell thickness of the hollow spheres can be controlled experimentally. The capacitive performance of the hollow structures was evaluated by using both cycle voltammetry and charge–discharge methods. The results demonstrated a specific capacitance as high as 184 F/g at a current density of 125 mA/g. The good electrocapacitive performance resulted from the mesoporous structure and high surface area of the MnO2-based hollow spheres.