The reasonable design of the composition and hollow structure of electrode materials is beneficial for promoting the electrochemical properties and stability of electrode materials for high-performance supercapacitors, and it is of great significance to understand the inherent effect of these features on their performance. In this paper, the amorphous Ni-Co double hydroxide nanocages with hollow structures (Ni-Co ADHs) including quasi-sphere, cube and flower are delicately tailored via a Cu2O template-assisted approach. By combining experimental characterization and density functional theory (DFT) calculations, we systematically study the morphological growth of Cu2O templates under different conditions and the electrochemical performance of Ni-Co ADHs. Due to the coordination and synergistic effect between different components, the unique hollow structure and the nature of amorphous materials, Ni-Co ADHs deliver a high specific capacitance of 1707 F g-1 at 1 A g-1. The DFT calculations demonstrate that Ni-Co ADH nanocages exhibit an optimal redox reaction energy barrier and immensely promote the performance. In addition, a hybrid supercapacitor assembled with Ni-Co ADHs as a cathode and active carbon (AC) as an anode shows a high energy density of 33.8 W h kg-1 at a power density of 850 W kg-1 and exhibits an excellent cycling performance with a retention rate of 98% after 50 000 cycles. The successful synthesis of Ni-Co ADH nanocages, combined with rational computational simulations, indicates the excellent electrochemical performance and the potential utilization of amorphous hollow nanomaterials as electrodes for supercapacitors.