The effect of two substituent groups, ortho-methoxy (-OCH3) and methyl (-CH3) in aniline, have been studied for supercapacitor applications. The polyaniline (PANI), poly (o-anisidine) (POA) and poly (o-toluidine) (POT) have been synthesized by oxidative polymerization method, and characterized by Cyclic Voltammetry (CV), UV–visible spectroscopy, Raman spectroscopy, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) techniques. The specific capacitance, charging/discharging and electrochemical impedance characteristics of the supercapacitor fabricated using PANI, POA, as well as POT electrodes are evaluated in 2M H2SO4 electrolytic media. The highest specific capacitance of 400 F/g is calculated for PANI, whereas, POA and POT have exhibited 360 F/g and 325 F/g capacitance in supercapacitor studies.