In this paper, novel reduced graphene oxide (rGO) composites (DAPrGOs) modified by diaminopyrene (DAP) were successfully synthesized via a facile solvothermal reaction method and used for supercapacitors. Compared with the pristine rGO, the DAPrGO1 electrode showed distinctly better performance (397.63 F g⁻¹ vs. 80.29 F g⁻¹ of pristine rGO at 0.5 A g⁻¹) with small charge transfer resistance. When a symmetric device was fabricated using DAPrGO1 as the active material, it also exhibited a high capacitance of 82.70 F g⁻¹ at 0.5 A g⁻¹ with an energy density of 25.84 W h kg⁻¹ at a power density of 375 W kg⁻¹, and even offered a high power density of 7500 W kg⁻¹ (18.71 W h kg⁻¹) at 10 A g⁻¹. Moreover, the device possessed good electrochemical stability up to 20 000 cycles, implying promising applications in energy storage fields.