The design of multicomponent electrode materials is attractive for advanced supercapacitors due to synergistic and multifunctional effects among different active materials. We reported here a structure-designed synthesis strategy to controllably fabricate hierarchical NiCoO@NiO composites on carbon fiber paper. The hierarchical structure with NiCoO core and NiO shell provided more active sites for ion transportation and storage to improve utilization rate of electrode materials, enhancing the specific capacitance and rate performance. As an ideal electrode material for supercapacitors, the NiCoO@NiO electrode exhibit high specific capacitance (1188 F/g at 2 A/g), excellent rate capability with ∼85% capacitance retained at 10 A/g, and compelling cycling performance (∼106.8% of the initial capacitance retention over 7000 cycles). The present work demonstrated a structure-designed strategy to construct high-performance multicomponent electrode materials for supercapacitors.