A polymer electrolyte membrane is considered as the heart of fuel cells. Here we report the preparation of proton exchange membranes (PEMs) of poly (vinylidene fluoride) (PVDF) blend poly (methyl methacrylate)-co-poly (sodium-4-styrene sulfonate) (PMMA-co-PSSNa) by solvent evaporation method. Three different types of PEMs have been prepared by using different ratios of PVDF and PMMA-co-PSSNa copolymer. We have investigated the effect of concentration of PVDF on water uptake, ion exchange capacity, mechanical, thermal, and oxidative stability, proton conductivity (K^m), and methanol permeability (P_M) of the blend membranes. These blend PEMs showed good physicochemical and electrochemical properties along with thermal and oxidative stability. The membrane prepared from PVDF (45% w/w) to PMMA-co-PSSNa (55% w/w) exhibited optimum P_M at room temperature (8.38 × 10⁻⁷ cm²s⁻¹). This low fuel crossover and high relative selectivity can make our prepared blend membranes a potential candidate in polymer electrolyte membrane fuel cells (PEMFCs) or direct methanol fuel cells (DMFCs).