<p>Proton exchange membrane is a crucial component of fuel cell technology and can be extensively applied as sustainable energy source in the respective sector. In this context, a new class of ionically crosslinked polyelectrolyte hydrogels (APV-1 to APV-5) are prepared, comprising various biopolymers and polyvinyl alcohol. Phosphoric acid is used as a dopant and then respective materials are evaluated as proton exchange membranes (PEMs). As prepared PEMs are analyzed for their functional groups, thermal stabilities and glass transition temperature using ATR-FTIR, TGA-DTG and DSC techniques, respectively. Morphological variations are detected via optical and scanning electron microscopy. Key physicochemical properties relevant to PEM material such as fluid uptake, ion-exchange capacity, surface charge, chemical and mechanical stability are also studied. Electrochemical behavior is measured via electrochemical impedance spectroscopy (EIS), revealing proton conductivity ranging from 0.06 to 1.90 mS cm⁻¹. Density functional theory (DFT) calculations are conducted to evaluate global quantum molecular descriptors (QMDs) and molecular electrostatic potential (MESP). These calculations help investigate the chemical interactions between precursor materials and assess their stability. The outstanding experimental results, along with affordable and simple synthesis suggests that these new membrane systems could be a viable eco-friendly option for PEMFC application.</p> Graphical Abstract <p></p>