In the present work, we report high temperature performance of solid electrolyte supercapacitor based on activated carbon (AC) and phosphoric acid doped poly [2,5 benzimidazole] (ABPBI). Supercapacitors with varying concentrations of solid electrolyte in the electrode were fabricated and unit cells were analyzed over a wide temperature range of 27–120°C. Supercapacitor with AC/ABPBI wt ratio 1.0:0.25 exhibited a specific capacitance of 197Fg−1 at room temperature. To the best of our knowledge, the value reported here is one of the highest for electric double layer supercapacitor with a solid electrolyte. The specific capacitance of supercapacitors having various compositions increased with temperature. The specific capacitance for AC/ABPBI wt ratio 1.0:0.25, capacitance increased to 248Fg−1 at 120°C. The performance of supercapacitors was also analyzed by electrochemical impedance spectroscopy. The Nyquist plots at room temperature and 100°C were studied by fitting them using Randles equivalent circuit. Supercapacitor with AC/ABPBI wt ratio 1.0:0.25 showed phase angle of 86.8° at low frequency which indicated excellent capacitive behavior at room temperature. The supercapacitor was found to have good stability during galvanostatic charge–discharge cycling even after repeated heating and cooling.