In this paper, a novel NiCo2S4@NiWO4honeycomb core-shell nanorod array significantly improved the electrochemical storage properties of supercapacitors. The characteristic architecture of the NiCo2S4@NiWO4electrode showed a remarkable specific capacity of 1273.5 C g−1at a current density of 1 A g−1. The asymmetric supercapacitor (ACS) had a high specific capacitance of 1502.4 C g−1at a current density of 1 A g−1as well as excellent cycling stability at a current density of 10 A g−1(101.25 % cycling retention rate after 10,000 cycles), and an energy density of 334 Wh kg−1with a power density of 2.38 kW kg−1. The research emphasized that a strong electronic coupling effect was observed at the interface of NiCo2S4and NiWO4and electron transfer from Ni-W-O to Ni-Co-S occurred around the interface, which further improved the electron transfer properties of electrode materials and hit the mark extends the life of the electrode and significantly improves the performance of energy storage systems.