There is a huge demand especially for polyvinylidene fluoride (PVDF) and its copolymers to provide high performance solid polymer electrolytes for use as an electrolyte in energy supply systems. In this regard, the blending approach was used to prepare PVDF-based proton exchange membranes and focused on the study of factor affecting their proton conductivity behavior. Thus, a series of copolymers consisting of poly (methyl methacrylate) (PMMA), polyacrylonitrile (PAN), and poly(2-acrylamido-2methyl-l-propanesulfonic acid) (PAMPS) as sulfonated segments were synthesized and blended with PVDF matrix in order to create proton transport sites in PVDF matrix.It was found that addition of PMMA-co-PAMPS and PAN-co-PAMPS copolymers resulted in a significant increase in porosity, which favored the water uptake and proton transport at ambient temperature. Furthermore, crystallinity degree of the PVDF-based blend membranes was increased by addition of the related copolymers, which is mainly attributed to formation of hydrogen bonding interaction between PVDF matrix and the synthesized copolymers, and led to a slight decrease in proton conductivity behavior of blend membranes. From impedance data, the proton conductivity of the PVDF/PMMAco-PAMPS and PVDF/PAN-co-PAMPS blend membranes increases to 10 and 8.4 mS cm −1 by adding only 50% of the related copolymer (at 25°C), respectively. Also, the blend membranes containing 30% sulfonated copolymers showed a power density as high as 34.30 and 30.10 mW cm −2 at peak current density of 140 and 79.45 mA cm −2 for the PVDF/PMMA-co-PAMPS and PVDF/PAN-co-PAMPS blend membranes, respectively. A reduction in the tensile strength was observed by the addition of amphiphilic copolymer, whereas the elongation at break of all blend membranes was raised. up, low operation temperature, and simplicity. Polymer electrolyte membrane (PEM), as one of the important parts of a PEMFC, has attracted a considerable attention. The performances of this part of PEMFCs are affected by its proton conductivity, electrical insulating, chemical and thermal stability, electro-osmotic drag coefficient, and good mechanical properties. Perfluorinated polymer membrane, known as Nafion, has been widely used as the proton exchange membrane in PEMFCs due to its excellent performances and stabilities. 6 However, the main limitation of Nafion is its high cost and decreasing proton conductivity at temperature above 100°C and low humidity condition, which limit its application. For this reason, introducing a new polymeric membrane is one of the key issues and research priorities in the field of PEMFCs.Recently, there is an enormous request especially for polyvinylidene fluoride (PVDF) and its copolymers to prepare superior PEM for PEMFC application. 2,7-9 An account of a great backbone similarity between PVDF and commercial perfluorinated membranes such as Nafion, Dow, Aciplex, and Flemion membranes, the study of PVDF and its copolymers as a replacement for the costly fluorinated membranes has become one of the research pri...