Hierarchically ordered mesoporous carbon/graphene (OMC/G) composites have been fabricated by means of a solvent-evaporation-induced self-assembly (EISA) method. The structures of these composites are characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy and nitrogen adsorption–desorption at 77 K. These results indicate that OMC/G composites possess the hierarchically ordered hexagonal p6mm mesostructure with the lattice unit parameter and pore diameter close to 10 nm and 3 nm, respectively. The specific surface area of OMC/G composites after KOH activation is high up to 2109.2 m² g⁻¹, which is significantly greater than OMC after activation (1474.6 m² g⁻¹). Subsequently, the resulting OMC/G composites as supercapacitor electrode materials exhibit an outstanding capacitance as high as 329.5 F g⁻¹ in 6 M KOH electrolyte at a current density of 0.5 A g⁻¹, which is much higher than both OMC (234.2 F g⁻¹) and a sample made by mechanical mixing of OMC with graphene (217.7 F g⁻¹). In addition, the obtained OMC/G composites display good cyclic stability, and the final capacitance retention is approximately 96% after 5000 cycles. These ordered mesopores in the OMC/G composites are beneficial to the accessibility and rapid diffusion of the electrolyte, while graphene in OMC/G composites can also facilitate the transport of electrons during the processes of charging and discharging owing to its high conductivity, thereby leading to an excellent energy storage performance. The method demonstrated in this work would open up a new route to design and develop graphene-based architectures for supercapacitor applications.