Hierarchical composites of sulfonated graphene-supported vertically aligned polyaniline nanorods (sGNS/PANI) are successfully synthesized via interfacial polymerization of aniline monomers in the presence of sulfonated graphene nanosheets (sGNS). The FE-SEM images indicate that the morphologies of sGNS/PANI composites can be controlled by adjusting the concentration of aniline monomers. FTIR and Raman spectra reveal that aligned PANI nanorod arrays for sGNS/PANI exhibit higher degree of conjugation compared with pristine PANI nanorods. The hierarchical composite based on the two-electrode cell possesses higher specific capacitance (497 F g−1 at 0.2 A g−1), better rate capability and cycling stability (5.7% capacitance loss after 2000 cycles) than those of pristine PANI nanorods.