A polyaniline fibers (PANI-F)/ reduced graphene oxide (rGO) composite was synthesized by using self-assembly of PANI-F and GO followed by hydrothermal reaction. The morphology and structure of samples were characterized with scanning electron microscopy (SEM), Fourier transform infrared spectrometer (FT-IR)and X-ray diffraction (XRD).The electrochemical properties were characterized with cyclic voltammetry (CV), galvanostatic charge/discharge(GCD) and electrochemical impedance spectrum(EIS). It showed that the rGO was homogeneously coated on the surfaces of PANI-F, and a high specific capacitance of 517 F/g (based on PAGO10 composite) was obtained at a current density of 1 A/g, compared with 378 F/g for PANI-F. Most of all, a high specific capacitance of 356 F/g was obtained at a current density of 10 A/g, compared with 107 F/g for PANI-F.