Graphene oxide/polypyrrole (GO/PPy) composite is synthesized by in situ oxidation polymerization of pyrrole (Py) in the presence of GO and used for supercapacitor electrode. The scanning electron microscope (SEM) observes that PPy nanoparticles are uniformly grown on the surfaces of GO sheets, leading to increase both the specific surface area and the electrical conductivity of material. GO/PPy composite exhibits better electrochemical performances than the pure individual components. When the mass ratio of GO to Py is 10:100, the GO/PPy composite electrode shows the highest capacitance of 332.6 F g−1, and presents high rate capability. An asymmetric supercapacitor is fabricated by using the optimized GO/PPy composite as positive electrode and activated carbon (AC) as negative electrode. The asymmetric supercapacitor can be cycled reversibly in the voltage range of 0–1.6V, and exhibits the maximum energy density of 21.4 Wh kg−1 at a power density of 453.9Wkg−1. Furthermore, the GO/PPy//AC asymmetric supercapacitor displays good rate capability and excellent cyclic durability.