In this study, we devised an easy and simple approach to synthesize a composite of flower-like cobalt–nickel–tungsten–boron oxides (Co–Ni–W–B–O) that were doped with reduced graphene oxide (rGO); the composite was designed for supercapacitor applications. A Co–Ni–W–B alloy was first deposited on rGO through one-pot chemical reduction in an ethanol solution at room temperature. The resulting Co–Ni–W–B alloy self-oxidized in air on the rGO surface. The Co–Ni–W–B–O/rGO composites resembled three-dimensional flowers with a high surface area; they also exhibited superior electrochemical performance when compared to most previously reported electrodes based on nickel–cobalt oxides. Furthermore, the Co–Ni–W–B–O/rGO composite prepared in an ethanol solution showed much higher electrochemical performance than the composite prepared in water. The Co–Ni–W–B–O/rGO electrode showed an ultrahigh specific capacitance of 1189.1 F g⁻¹ at 1 A g⁻¹ and exhibited a high energy density of 49.9 W h kg⁻¹ along with remarkable cycle stability (10 000 cycles with 80.7% capacitance retention at 15 A g⁻¹), which is promising for its application in energy storage devices.