In the present work, poly ortho aminophenol/copolyimides (POAP/PI) composites were prepared using PIs together with POAP. PIs were synthesized using different molar ratios of diamines and dianhydride by polymerization method. Different electrochemical methods including cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and electrochemical impedance spectroscopy (EIS) were applied to study system performance. Presence of PIs in the composite films improved mechanical and electrochemical performance of the p-type conductive polymer. This study reveals that POAP/PI with high specific capacitance and long cycle-life is suitable for application in energy storage materials.