Proton-conducting and methanol barrier properties of the proton exchange membrane (PEM), as well as the high cost of direct methanol fuel cell (DMFC) components, are the key determinants of the performance and commercialization of DMFCs. Therefore, this study aimed to develop cost- and performance-effective membranes based on sulphonated poly (vinyl chloride) (SPVC)/poly (2-acrylamido-2-methyl-1-propane sulphonic acid) (PAMPS) blends. Such membranes have been simply prepared by blending SPVC and PAMPS solutions, followed by solvent evaporation via casting. Interaction of SPVC with PAMPS was confirmed by different characterization techniques such as Fourier Transform Infra-red (FTIR) and Raman scattering spectroscopy in which the two characteristic absorption bands of sulfonic groups appeared at 1093 and 1219 cm−1 additionally, strong peaks at around 1656 cm−1 attributed to vibration of amide groups of PAMPS portion in the polymer blend. Furthermore, the interaction of SPVC with PAMPS improves the thermal properties along with ion exchange capacity in turn decreasing the methanol permeability through the membrane in comparison with the SPVC membrane. The IEC of PVC and Nafion 117 membranes were 1.25, 0.91 meq/g; respectively. And the maximum water uptake of PVC and Nafion 117 membranes were 75 and 65.44%; respectively. Methanol permeability value of 7.7 × 10−7 cm2/s which was noticeably lower than the corresponding value recorded for Nafion® (3.39 × 10−6 cm2/s). Therefore, these fabricated membranes can be considered a low-cost efficient candidate for use in DMFC, especially for its capability to resolve the methanol cross-over issue.