Homogeneous cation-exchange membranes were prepared through evaporation and phase inversion methods using sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO) and sulfonated polyvinylchloride as binders. The effect of polymers blend’s ratio and preparation method on structure and electrochemical properties of the prepared membranes were evaluated. The microstructures of the membranes were investigated by scanning electron microscopy (SEM) and the sulfonation of polyvinylchloride was confirmed by elemental analyses. Moreover, the membranes performance was evaluated by ion-exchange capacity (IEC), fixed ion concentration, membrane potential, transport number, permselectivity, areal resistance, ionic permeability, flux of ions, current efficiency, membrane oxidative stability, mechanical properties and water content tests. The results indicated that IEC and water content were affected by the SPPO content and microstructures of the membranes. The results showed increased efficiency and suitable electrochemical properties for membranes prepared by the evaporation method in comparison with others. Also, Fe2O3 nanoparticles were synthesized at room temperature by a simple sonochemical reaction between ferric chloride and NaOH. The results revealed that the addition of different amounts of Fe2O3 nanoparticles to the polymeric matrix could affect the hydrophilicity and transport properties of ion-exchange .membranes