The conductive composites were prepared from pyrrole (Py) and 4-sulfonic diphenylamine (SD) by chemico-oxidative method using graphene (RGO) as the dopant. Through orthogonal test and dispersive test, we found the best conditions of synthesizing the composites were as follows: the oxidant is FeCl3･6H2O, the mole ratio of oxidant and monomer is 1:1, the mole ratio of Py and SD is 7:3(total amount is 0.01 mol), the doping amount of graphene is 0.05 g; Under the above conditions, the conductivity of the composite was 12.05 S/cm, and it had better dispersion in water. The composites were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The thermal stability of the composites was tested by Thermal Gravimetric Analyzer (TGA). Results showed that the structure unit of SD was successfully embedded in the molecular chain of the polypyrrole (PPy), conductivity and thermal stability of the composites were significantly improved by the doping of RGO. Meanwhile, the composite was added as conductive filler to the waterborne polyurethane to study antistatic performance and mechanical properties of the coating, the comprehensive performance of the coating is better and the surface resistivity of the film can reach 8.65×107 Ω when the added amount is 4%.