Unique molybdenum trioxide decorated nickel-cobalt oxide nanostructures (MoO3/NiCo2O4-NSs) and three-dimensional hierarchical structure α-FeOOH/rGO film were prepared via facile hydrothermal and annealing strategies. Owing to the merits of the large surface area, superior ionic conductivity, increased availability of active sites/interfaces, rich mixed valences of polymetallic oxide and the favorable structural stability, the as-prepared optimized battery-type MoO3/NiCo2O4-NSs electrode material presents an extraordinary specific capacity (1042 F g−1 at 1 A g−1), largely improved rate capability (93%, from 1 to 6 A g−1), and superior cycling performance, compared with the NiCo2O4–NCs, MoO3, and also exceeds some of the reported Ni-, Co-based electrodes. Underlying such great improvement, a MoO3/NiCo2O4-NSs//α-FeOOH/rGO asymmetric supercapacitor device with a large potential window was assembled, which delivered a high capacitance of 141 F g−1 at 1 A g−1, an excellent energy density of 50.2 Wh kg−1, and an amazing power density of 4.8 kW kg−1. The serially connected asymmetric supercapacitor can power commercial light-emitting diodes suggesting their potential application for electronic gadgets. The superior energy storage characteristics of the asymmetric supercapacitor are strongly attributed to the interconnected 3D nanoporous network architectures of the MoO3/NiCo2O4-NSs and the good compatibility with the α-FeOOH/rGO negative electrode.