The electrode composites composed of conductive polypyrrole and graphene for electrochemical capacitors have attracted extensive attention due to their potential application. Here a green synthesis method was used to fabricate hierarchical nanostructured polypyrrole/graphene composites by using vitamin C as a reducing agent. The as-prepared nanocomposites were characterized by FTIR, Raman, XRD, TGA, SEM and TEM techniques. The results showed that the polypyrrole chains in the PPy/rGO-CTAB composite successfully inserted into the two-dimensional space of graphene layers. In addition, the electrochemical performances of composites were measured with cyclic voltammetry (CV), galvanostatic charge–discharge (GCD) and electrochemical impedance spectroscopy (EIS) experiments. The results indicated that PPy/rGO-CTAB composites possessed better thermal stability, higher specific capacitance, lower resistance, relatively better cyclic properties and faster response to oxidation/reduction than both PPy/rGO composites without addition of CTAB and rGO.