Abstract: The combination of polypyrrole (PPy) with a unique doping structure and graphene (GE) aerogel with a rich porous structure can realize the complementary advantages of the two materials. Triphenyl blue (TB) doped GE/PPy composite aerogel was prepared by one-step hydrothermal method. The SEM, FTIR, XRD, Raman spectroscopy and XPS were used to characterize the morphological structure, chemical structure, and doping structure of the composite electrode material. The results showed that TB doped GE/PPy composite aerogel provided three porous network structure. Conductive PPy can be successfully polymerized as graphene oxide (GO) was reduced in the composite hydrogel. Due to the introduction of TB, the doping level of the composite hydrogel has been increased. The electrochemical tests demonstrated that the prepared TB-5/PPy-GO (TB concentration of 5 mmol·L⁻¹) aerogel exhibited superior specific capacitance of 392 F·g⁻¹ at 1 A·g⁻¹. The capacitance retention rate can reach 85% after 10 000 cycles. The hybrid device, which was assembled with TB-5/PPy-GO and active carbon as positive and negative electrode, respectively, demonstrated maximum energy of 35.89 W·h·kg⁻¹ at 400 W·kg⁻¹, suggesting its good supercapacitive performances.