In this work proton exchange membranes were prepared by a modified microwave casting solution technique, using the polymers blend (polyethersulfone (PES), polystyrene (PS), polyvinylidenefluride (PVDF)). Modified casting method was used to overcome the poor compatibility between hydrophilic, (PES, PS) and hydrophobic PVDF, by cooling the substrate during the film casting process to (4.5-5.5^oC). Membranes were chemically modified by three reaction types to study the differences between their effects on the required properties for microbial fuel cell application. These methods use blend organic sulfonic acid precasting process and sulfonation by sulfuric acid post-casting process (APS), blending organic sulfonic acid precasting process (AS) and sulfonation by sulfuric acid post-casting process (AP). The presence of organic sulfonic acid and the sulfonation were confirmed via FTIR spectra for the membranes. The membranes were characterized by proton conductivity, ion exchange capacity (IEC), [-SO₃H] value, and water uptake. MFC is characterized by electrochemical polarization tests and power densities obtained from it were used to evaluate the efficiency of the membrane in the cell.