In this paper, MnO2 nanomaterials of different crystallographic types and crystal morphologies have been selectively synthesized via a facile hydrothermal route and electrochemically investigated as the cathode active materials of primary and rechargeable batteries. beta-MnO2 nano/microstructures, including one-dimensional (1-D) nanowires, nanorods, and nanoneedles, as well as 2-D hexagramlike and dendritelike hierarchical forms, were obtained by simple hydrothermal decomposition of an Mn(NO3)(2) solution under controlled reaction conditions. alpha-and gamma-MnO2 nanowires and nanorods were also prepared on the basis of previous literature. The as-synthesized samples were characterized by instrumental analyses such as XRD, SEM, TEM, and HRTEM. Furthermore, the obtained 1-D alpha- gamma-MnO2 nanostructures were found to exhibit favorable discharge performance in both primary alkaline ZnMnO2 cells and rechargeable Li-MnO2 cells, showing their potential applications in high-energy batteries.