The rational design and construction of efficient electrodes for applications in energy storage have been widely conducted. In this work, we have demonstrated a binder-free electrode composed of Co3O4@Co–Ni-sulfides core/shell nanowire arrays with tunable Ni/Co ratio for the high-performance pseudo-capacitors. This as-fabricated electrode can offer the desired structural features for the efficient usage of active materials. With the advantages of the well-ordered architecture, this hierarchical electrode shows a high specific capacitance of 1844 F g−1 (7.38 F cm−2) at a current density of 5 mA cm−2. Besides, an asymmetric supercapacitor based on this synthesized electrode can deliver a maximum energy density of 44.8 Wh kg−1 and a good cycling stability of 91% retention after 4000 cycles. Our results presented here demonstrate that this hierarchical electrode has potential usage in electrochemical energy storage.