Abstract: Taking the graphite oxide as the supporter, using sodium lignosulphonate as the dopant and ferric chloride as the oxidant, the polypyrrole(PPy)/graphite oxide composite was prepared by the chemical in-situ polymerization of pyrrole monomer in the graphite oxide layers. The phase composition, structure and morphology were characterized by XRD, FTIR and SEM, respectively. The thermal stability of the composite was analyzed by TGA. The electrochemical performance of the composites was examined through galvanostatic charge-discharge, cyclic voltammetry and electrochemical impedance technique. Results show that the PPy/graphite oxide composite synthesized by the chemical in-situ polymerization method is with a kind of "layer-ball" "sandwich" type microstructure so as to form a good conducting network. The synthesized composite is with high crystallinity, neat and less defects. And the pyrrole monomer in the composite materials is bonded with the oxygen containing functional groups of the graphite oxide by the keys of N-H. This kind of novel microstructure modeling of PPy/graphite oxide composite and the perfect chemical key connecting between them confirm it with high capacitance. The specific capacitances of the composites are 500, 460, 427 and 396 F/g at the current density of 0.5, 1.0, 2.0 and 5.0 A/g, respectively. Moreover, after 1000 cycles at the current density of 2.0 A/g, the capacitance retention of the PPy/graphite oxide composite is 97.2%.