Sulfonated polyvinylchloride (SPVC) cation exchange membranes were coated using chitosan solutions comprising different amounts of Fe3O4 nanoparticles. Influence of chitosan immobilization as well as nanofiller concentration on the electrochemical performance of the membranes was investigated. Electrochemical properties of the membranes including permselectivity, ionic permeability, and areal resistance were studied using an equipped electrodialysis setup and NaCl solution as model electrolyte. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were employed for membrane characterization. Electrochemical performance of the SPVC membranes was improved by coating chitosan polymer. In addition, ionic permeability and permselectivity of the membranes were initially raised by increasing nanoparticles concentration from nil to 2 wt% and then decreased by further insertion of the nanofiller. The areal resistance of the plain SPVC membrane was decreased from 9.4 to 2.9 (ohm) by coating of chitosan solution including optimum value of nano-Fe3O4 due to electrical potential field enhancement across the membrane.