This paper introduced a process to prepare the carbon nanosphere (CNS)/NiCo2O4 core-shell sub-microspheres. That is: 1) CNSs were firstly prepared via a simple hydrothermal method; 2) a layer of NiCo2O4 precursor was coated on the CNS surface; 3) finally the composite was annealed at 350 °C for 2 hours in the air, and the CNS/NiCo2O4 core-shell sub-microspheres were obtained. This core-shell sub-microsphere was prepared with a simple, economical and environmental-friendly hydrothermal method, and was suitable for large-scale production, which expects a promising electrode candidate for high performance energy storage applications. Electrochemical experiments revealed that the composite exhibited remarkable electrochemical performances with high capacitance and desirable cycle life at high rates, such as: 1) the maximum specific capacitance was up to 1420 F/g at 1 A/g; 2) about 98.5% of the capacitance retained after 3000 charge-discharge cycles; 3) the capacitance retention was about 72% as the current density increase from 1 A/g to 10 A/g.