Polymer electrolytes are known to possess excellent physicochemical properties that are very useful for electrochemical energy systems. The mobility in polymer electrolytes is understood to be mainly due to the segmental motion of polymer chains and the ion transport is generally restricted to the amorphous phase of the polymer. Gel polymer electrolytes (GPE) that are formed using plastizicers and polymers along with ionic salts are known to exhibit liquid-like ionic conductivity while maintaining the dimensional stability of a solid matrix. In the present study, the preparation and characterization of poly(vinyl alcohol)-based hydrogel membranes (PHMEs) as electrolytes for electrochemical capacitors have been reported. Varying HClO₄ dopant concentration leads to different characteristics of the capacitors. The EC comprising PHME doped with 2 M HClO₄ and black pearl carbon (BPC) electrodes has been found to exhibit a maximum specific capacitance value of 97 F g^-1, a phase angle value of 78°, and a maximum charge-discharge coulombic efficiency of 88%.