Nanomaterials with hollow shell structure were studied and used in environment and energy technology due to their high specific capacity and good cycling stability. In this study, Co3O4/NiCo2O4 double‐shelled nanocages (DSNCs) were synthesized. Firstly, ZIF‐67 (Zeolitic imidazolate framework) was synthesized at room temperature; then, a ZIF‐67/Ni−Co layered double shelled hydroxides (LDH) structure was synthesized by preparing the shell structure with the use of nickel nitrate. Finally, this LDH was calcinated at 350 °C to form Co3O4/NiCo2O4 DSNCs. Among the prepared electrodes, Co3O4/NiCo2O4‐2 DSNCs exhibited the largest specific capacity (236.18 C g−1), with high cycling stability (103.43 %, 5000 cycles). Meanwhile, the assembled Co3O4/NiCo2O4‐2//AC BSH device showed outstanding cycling stability, with a specific capacitance retention rate of 85.39 % and a good coulombic efficiency of 96.35 % even after 10000 cycles. Moreover, in oxygen evolution reaction (OER), Co3O4/NiCo2O4‐2 DSNCs also had a low Tafel slope and overpotential (158 mV). Co3O4/NiCo2O4 DSNCs with enhanced electrochemical performance demonstrate that the property of energy conversion and storage can be improved by preparation of hollow structure.