Abstract: Conductive polymers with good intrinsic conductivity and high charge density are considered as potential electrode materials for supercapacitors. However, it has been reported that the chains of polypyrrole and polyaniline could expand and contract during the charging and discharging process, leading to structural de-conformation. Poly(2-aminoazulene) is lately reported to present large area film morphology and remarkable electrical conductivity at room temperature. Nevertheless, relevant studies based on azulene as supercapacitor electrode materials have rarely been reported. Here, we report an all-solid-state supercapacitor based on a conductive polymer, poly(2-aminoazulene), as the electrode material. According to conventional electrochemical measurement, poly(2-aminoazulene) film-based device exhibits promising capacitive performance in the operating voltage window of −0.2—0.8 V: maximum volumetric capacitance of 83 F/cm³ and maximum areal capacitance of 0.54 mF/cm², maximum energy density of 11.6 mW·h/cm³ and maximum power density of 3304 W/cm³. In addition, the supercapacitor retains 95.1% of the initial capacitance after 1000 cycles, indicating good cycling stability which enables its reliability during practical applications. These results not only prove that poly(2-aminoazulene) could be next generation candidates of all-solid-state supercapacitor electrode materials but also provide a new strategy for exploration of intrinsic conductive polymers for energy storage.