MnO2 with novel mesoporous structure has been firstly synthesized via a simple in situ reduction process by using different carbon materials as sacrificed template and reducing agent. The morphology and microstructure of as-synthesized mesoporous MnO2 were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), nitrogen adsorption and desorption experiments. The results demonstrate that porous MnO2 prepared using mesoporous carbon as template has very large specific surface area and uniform pore-size distribution. The electrochemical measurements showed that novel porous MnO2 have higher capacity (221Fg−1) with excellent rate and higher capacity retention as electrochemical capacitors (ECs) electrode materials, which may be attributed to the unique nanostrcture of porous MnO2. These all imply that MnO2 with novel mesoporous structure has been attractive for practical and large-scale applications in mobile equipment.