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The development and optimization of electrocatalysts is one of the key points to reduce the energy barrier of electrocatalytic water splitting and improve the kinetics of electrocatalytic reactions. It is necessary to develop low-cost, high-performance electrocatalysts with large-scale application prospects. In order to solve this problem, hybrid structured ZnCo2O4@Co3O4 nanowires are successfully synthesized through hydrothermal synthesis and electrodeposition. As electrocatalysts for water splitting, ZnCo2O4@Co3O4 can reach a current density of 50 mA cm−2 at an overpotential of 278 mV for the OER and 166 mV@−10 mA cm−2 for the HER, which could be higher than that of single ZnCo2O4 and Co3O4. At the same time, ZnCo2O4@Co3O4 samples also exhibit a cell voltage of 1.67 V at a high current density of 50 mA cm−2 and superior durability for 50 h. The fabricated product also showcases a specific capacitance of 1316 F g−1 at 1 A g−1. Additionally, the assembled device attains a maximum energy density of 47.3 W h kg−1 at a power density of 1126 W kg−1. Furthermore, density functional theory (DFT) calculation further confirms that the heterostructure can significantly promote Gibbs free energy for hydrogen adsorption. And the significant increase in the density of total states (DOS) also enhances the catalytic activity for the HER. [ABSTRACT FROM AUTHOR]