Numerous efforts have been made to investigate manganese oxides as active materials in the field of energy storage. To further explore the full use of MnO2 for supercapacitor in aqueous electrolyte, a facile two-step hydrothermal method are developed to synthesis T-Nb2O5@MnO2 composites supported by carbon cloth (CC). With the hierarchical nanostructure and rational synergistic effect, CC@T-Nb2O5@MnO2 exhibits a high specific capacitance (319Fg−1 at 0.2Ag−1) and a good cycling stability (85.7% retention after 2000 cycles). An asymmetric supercapacitor with CC@T-Nb2O5@MnO2 nanocomposite as positive electrode and activated graphene oxide as negative electrode yielded an energy density of 31.76Whkg−1 and a maximum power density of 2250Wkg−1. These delightful findings demonstrate CC@T-Nb2O5@MnO2 to be a nice electrode material, and meanwhile provide an idea to design novel structure with synergic mechanism for high-performance supercapacitors.