Co3O4-based materials are regarded as superior electrode candidates in various energy storage devices due to their high theoretical capacity. Unfortunately, the poor electronic conductivity and huge volume expansion hamper their widespread applications. Therefore, nano-processing and introducing conductive matrix can view as the necessary methods to make Co3O4-based materials better for an advanced supercapacitor electrode. Herein, a dual-template nanocasting technique is proposed to design the ultrafine Co3O4 grains highly-dispersed on the reduced oxide graphene nanosheets (Co3O4/rGO-C), in which cetyltrimethyl ammonium bromide and silicate species are hired as the ideal soft and hard template, respectively. Co3O4 grains with size <10 nm can expose more active sites and thus exert more redox activities to enhance the capacitive performance. In additional, ∼4 nm moderate pores are obtained in Co3O4/rGO-C after the hard template removing, which provides more diffusion channels for ion/electron rapid transport and also effectively alleviates the volume expansion on cycling. Consequently, the Co3O4/rGO-C electrode exhibits a remarkable specific capacitance (709.1 F g−1 at 1 A g−1) and long-term endurance (91.2% after 6000 cycles). Furthermore, an assembled solid-state asymmetric device of Co3O4/rGO-C||rGO delivers a super-high energy-density of 48.2 Wh kg−1 at 750.5 W kg−1. The high energy-density assists two devices in lightning a red light-emitting diode for 340 s. These results evidence the nanocasting strategy as an efficient method to achieve the advanced electrode materials for energy storage devices.