 This study introduces a novel, non-toxic, scalable, two-step method for the fabrication of highly nanoporous nickel and nickel oxide (Ni–NiO) foam/Electrochemically reduced graphene oxide (ERGO) electrodes with exceptional capacitance suitable for supercapacitor application. This procedure includes drop cast and graphene oxide (GO) reduction by galvanostatic process. To create the electrodes, electrodeposition process and selective electrochemical dealloying accompanied by a hydrogen evolution reaction (HER) were performed on a copper substrate. Afterwards, drop cast and galvanostatic processes were accomplished to coat GO nanosheets on Ni–NiO foam. The structure of achieved nanocomposites was investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). High-specific capacitance of 1995 F g−1 at a current density of 1 A g−1 (galvanostatic charge–discharge) (GCD) was achieved for the Ni–NiO foam/electrochemically reduced graphene oxide (ERGO) electrode with excellent cycling stability. A constant, high-specific capacitance (95.1% of the initial value) was achieved after 6000 cycles at 20 A g−1.