A novel proton exchange membrane consisting of 2-N-acrylamido-2-methyl −1-propane sulfonic acid modified graphene oxide nanocomposite (PAMPS-mGO), carboxylated poly(vinyl chloride) (CPVC), and poly 2-N-acrylamido-2-methyl−1-propane sulfonic acid (PAMPS) has been successfully prepared by simple and scalable polymer blending methodology. Different compositions of PEM in terms of its constituting precursors such as PAMPS-mGO, CPVC, and PAMPS were optimized by Placket Burman Design and their ion exchange capacity (IEC), oxidative stability, water uptake percentage, mechanical stability, and proton conductivity were evaluated. The amounts of significant precursors were further optimized by Central Composite Design. The membrane with excellent performance in PEMFC was obtained when appropriate proportions of CPVC (10%), PAMPS (20%), and PAMPS-mGO (20%) were blended. Among all membrane with mentioned composition exhibited IEC 1.3 mmol/g, oxidative stability 97.2%, WU 40.8%, proton conductivity 151 S/cm, water content 17.43, current density 1537 mA/cm 2 at 120 C, power density 566.5 mW/cm 2 at 120 C, Young modulus 797 MPa, tensile strength 16.8 MPa, and elongation at break % of 2.7 MPa. These results are in good comparison with PEM based on Nafion. Thus, the CPVC, PAMPS, and PAMPS-mGO-based composite PEM is a good candidate for PEMFC at elevated temperature under anhydrous conditions.