In this research, the fabrication of a hybrid structure of polyaniline hollow fibers (PANI-HF) and reduced graphene oxide (rGO) has been reported and the hierarchical structure and electrochemical performance of the system has also been studied. The formation of the hierarchical hybrid structure has been proved by scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM), fourier transform infrared (FTIR), and X-ray diffraction (XRD). Cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), electrochemical impedance spectroscopy (EIS) and cyclic stability were employed to evaluate the electrochemical performance of the composites. PANI-HF has provided a superior structure for enhanced electrocapacitance due to its higher specific surface area. Decorating the PANI-HF by rGO sheets has resulted in better specific capacitance (C-s) at high scan rates. At the scan rate of 20 mV s(-1), the specific capacitance of PANI-HF/rGO hybrid was found to be 449 F g(-1) while it was 425 F g(-1) for PANI-HF. Furthermore, rGO has provided a solid network in hybrid sustaining PANI-HF during the long-term charge-discharge cycles and improved the cyclic stability. In addition, only 16% of the initial capacitance of PANI-HF/rGO hybrid has been lost after 2000 cycles.