Poly(ortho-aminophenol)/graphene nanocomposite was electrochemically synthesized. The nanocomposite represented an excellent supercapacitive behavior resulted from the complementary properties of graphene and the conducting polymer. The nanocomposite was characterized by various methods including scanning electron microscopy, transmission electron microscopy, FT-IR spectroscopy, X-ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy techniques. As an electrode material, the specific capacitance of the nanocomposite was 281.1Fg−1 which was about 3times of the specific capacitance of graphene. This behavior was related to a synergistic effect of the electrical double layer capacitance of graphene and pseudo-capacitance of the conducting polymer. The nanocomposite kept >99% of the initial specific capacitance after 1200 charge/discharge cycles at a current density of 1Ag−1.