A fibrous, flexible supercapacitor (FFSC) electrode with unique layer-by-layer structures is constructed using a one-step electrophoretic method. The highly enhanced capacitance of 53.56 mF/cm2 and good charge/discharge stability is attributed to the synergistic effect between the GO nano-sheet and carbon nano-sphere for electrolyte contact and ion transportation. Such construction method can be employed to construct various FFSC electrodes for portable energy storage and wearable electronics applications.