This paper studies the synthesis and electrochemical characterization of novel graphene-beaded carbon nanofibers (G/CNFs) as electrode material for use in supercapacitor. The porous G/CNF films were prepared by electrospinning polyacrylonitrile (PAN)/N,N-dimethylformamide (DMF) solution dispersed with oxidized graphene nanosheets, followed by carbonization at 800 °C in a tubular quartz furnace. The morphology and chemical structure of the porous G/CNF films were characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. The electrochemical behavior of the synthesized G/CNF films as supercapacitor electrodes was characterized by means of cyclic voltammetry (CV), galvanotactic charge/discharge, and electrochemical impedance test in a 6 m KOH aqueous electrolyte. Electrochemical measurements revealed that the maximum specific capacitance of the porous G/CNF electrodes reached up to 263.7 F g− 1 at a discharge current density 100 mA g− 1. Furthermore, the supercapacitor exhibited very good cycling stability of energy storage with the retention ratio of 86.9% after 2000 cycles. The high electrochemical performance of the G/CNF electrodes was attributed to the unique nanostructural configuration, high electrical conductivity, and large specific surface area of the graphene nanosheets.