Hierarchical NiCo₂O₄@Ni₃S₂ core/shell mesoporous nanothorn (NT) arrays were successfully designed and synthesized on the surface of Ni foam via a two-step process which includes hydrothermal synthesis and electrodeposition. The obtained core/shell nanostructures consist of NiCo₂O₄ mesoporous NTs as the core and interconnected Ni₃S₂ ultrathin nanosheets as the shell, which exhibit remarkable electrochemical performance for supercapacitors because of the heterogeneity synergies of the two components. Compared with the single component of either NiCo₂O₄ mesoporous NTs or Ni₃S₂ ultrathin nanosheets, the hierarchical NiCo₂O₄@Ni₃S₂ core/shell mesoporous NT arrays demonstrate a higher specific capacitance of 1716 F g⁻¹ at a current density of 1 A g⁻¹ and a better rate capability of 1104 F g⁻¹ at 20 A g⁻¹ while maintaining 83.7% capacity after 2000 cycles at a current density of 4 A g⁻¹. Such superior electrochemical performance may originate from the unique hierarchical core/shell nanostructures that would possess faster ion and electron transfer, enhanced reactivity and modified structural integrity.