In the present study, a novel PVA–g–PMA hybrid membrane was developed for application in direct methanol fuel cell (DMFC). Maleic anhydride (MA) was grafted on polyvinyl alcohol (PVA) both ionically and chemically using potassium persulfate (KPS), for the first time. ThePVA–g–PMA thus synthesized was then blended with 3–Amino–4–[3–(triethylammonium sulfonato)phenyl amino]phenylene hydrochloride. The prepared membranes were characterized by FT–IR, TGA. 0.0104 S/cm of proton conductivity was found for the membrane. The ion exchange capacity was found to be 2.175 meq/g and the water uptake capacity as 14.9%. The single-chamber fuel cell power density was higher (34.72 mW/cm2) and current density (62.11 mA/cm2) when compared to Nafion 117 membrane.