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This work has been focused on the synthesis and characterization of different blended membranes SPEEK-35PVA (Water), SPEEK-35PVA (DMAc) prepared by casting and nanofiber-reinforced proton exchange membranes Nafion-PVA-15, Nafion-PVA-23 and SPEEK/PVA-PVB. The two first reinforced membranes were made up of Nafion® polymer deposited between polyvinyl alcohol (PVA) nanofibers. The last composite membrane is considered because the PVA is a hydrophilic polymer which forms homogeneous blends with SPEEK suitable to obtain high proton conductivity, while the hydrophobic PVB can produce blends in a phase separation morphology in which very low water uptake can be found. The synthesized membranes showed an outstanding stability, high proton conductivity, and enhanced mechanical and barrier properties. The membranes were characterized in single chamber microbial fuel cells (SCMFCs) using electrochemically enriched high sodic saline hybrid H-inocula (Geobacter metallireducen, Desulfurivibrio alkaliphilus, and Marinobacter adhaerens) as biocatalyst. The best performance was obtained with Nafion-PVA-15 membrane, which achieved a maximum power density of 1053 mW/m3 at a cell voltage of 340 mV and displayed the lowest total internal resistance (Rint ≈ 522 Omega). This result is in agreement with the low oxygen permeability and the moderate conductivity found in this kind of membranes. These results are encouraging towards obtaining high concentrated sodic saline model wastewater exploiting MFCs.