In this paper, the core/shell Ni-P@Ni-Co composite with micro-/nanostructure, coating Ni-Co on the precursor Ni-P microspheres, has been synthesized successfully via facile two-step hydrothermal method. The chemical composition and microstructure of as-prepared samples were characterized by XRD, EDS, BET, XPS, SEM, and TEM. The results show that the core/shell composite Ni-P@Ni-Co, with a more rough surface and larger specific surface area (74.2 m(2) g(-1)) than bare Ni-P, exhibits good charge storage performance (the specific capacitance reaches up to 1221.1 F g(-1) at the current density of 1 A g(-1), 1.8 times of Ni-P under the same conditions), and good cycling performance (the retention of specific capacitance is 95.8% after 5000 cycles at 2 A g(-1) current density). To further evaluate the practical application property of Ni-P@Ni-Co, an asymmetric supercapacitor (Ni-P@Ni-Co//AC) was assembled, with the Ni-P@Ni-Co and activated carbon (AC) as the positive and negative electrodes, respectively. The electrochemical results reveal that Ni-P@Ni-Co//AC delivers a high energy density of 28.9 Wh kg(-1) at a power density of 0.4 kW kg(-1), along with a specific capacitance retention rate of 89.1% and nearly 100% Coulomb efficiency at a current density of 1 A g(-1) after 5000 cycles.