In this work, we report CoMoO4@MoZn22 core-shell structures grown on Ni foam via a simple hydrothermal route. The as-prepared products can be utilized directly as electrode materials for supercapacitors, demonstrating a capacity of 923 C g(-1). The as-assembled hybrid capacitor using CoMoO4@MoZn22 as positive electrode delivers an energy density of 129 Wh kg(-1) at a power density of 2740 W kg(-1) and a capacitance retention of 97% after 10,000 cycles. Moreover, the as-obtained products are also used as the alternative electrocatalysts, which shows a low overpotential of 240 mV at 20 mA cm(-2) for oxygen evolution reaction (OER). It suggests that the bi-functional CoMoO4@MoZn22 structures could be potential candidate materials for future energy storage devices and electrocatalysts.