An exceptional hierarchical nanostructured MnO2/carbon hybrid was in situ generated by a mild wet chemical pre-treatment and then hydrothermal method. The thickness of the representative petal-like nanosheet was measured below 5 nm. Growth mechanism of the achieved hierarchical hybrid is associated with simultaneously occurred redox and oxidation-intercalation reactions. The surface layers of carbon black (XC-72) were partly exfoliated, and redox reaction between KMnO4 and hydroxyl group occurred on the both side of these layers, resulting in the hierarchical hybrid of MnO2/carbon. (C) 2013 Elsevier B.V. All rights reserved.