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Co3O4 nanomaterials are grown in situ on nickel foam by a facile two-step method, and their electrochemical properties for supercapacitors and electrochemical H2 production are systematically investigated. As an electrode material for supercapacitors, the Co3O4/NF nanomaterials have a specific capacitance of 4705 mF/cm2 at a current density of 2.5 mA/cm2 in 6 M KOH solution with good cycling stability. The asymmetric supercapacitor assembled with Co3O4/NF (positive) and activated carbon (negative) exhibits high energy storage capacity (2023 mF/cm2 at 5 mA/cm2), good rate performance and cycling stability. In addition, the Co3O4/NF nanocomposites exhibit excellent catalytic performance in electrolytic aquatic hydrogen. In 1 M KOH electrolyte, a potential of only 225 mV is required to provide a current density of 30 mA/cm2. Furthermore, increasing the temperature enhances the catalytic performance of the material, which provides the possibility of using industrial production waste heat to catalyze hydrogen production. Therefore, this study not only shows the great potential of Co3O4/NF nanocomposites as a supercapacitor cathode material, but also indicates its great opportunity for hydrogen production. [ABSTRACT FROM AUTHOR]