Electrodes with rationally designed hybrid nanostructures can offer many opportunities for the enhanced performance in electrochemical energy storage. In this work, the uniform 2D Co₃O₄-based building blocks have been prepared through a facile chemical etching assistant approach and a following treatment of thermal annealing. The obtained nanosheets array has been directly employed as 2D backbone for the subsequent construction of hybrid nanostructure of Co₃O₄@NiMoO₄ by a simple hydrothermal synthesis. As a binder-free electrode, the constructed 3D hybrid nanostructures exhibit a high specific capacitance of 1526 F g^_1 at a current density of 3 mA cm^_2 and a capacitance retention of 72% with the increase of current density from 3 mA cm^_2 to 30 mA cm^_2. Moreover, an asymmetric supercapacitor based on this hybrid Co₃O₄@NiMoO₄ and activated carbon can deliver a maximum energy density of 37.8 Wh kg^_1 at a power density of 482 W kg^_1. The outstanding electrochemical behaviors presented here suggest that this hybrid nanostructured material has potential applications in energy storage.