A new type of electrodialysis mixed matrix (MM) cation exchange membrane was prepared by incorporating carbon nanofibers (CNFs) into membrane matrix. The microscopy images showed uniform surface for the membrane relatively. The use of CNFs into membrane body enhanced membrane surface hydrophilicity, potential, transport number, permselectivity, and ionic conductivity obviously, while water uptake decreased. The sodium flux was also enhanced by incorporation of CNFs into membrane matrix from 0 to 0.5%wt and 2 to 8%wt, while declined for the samples in the range of 0.5 to 2%wt CNF ratios. Compared to pristine membrane, a smoother surface was observed for PVC-CNF membrane. Electrodialysis showed the (K+/Na+) flux ratio about 2.14. The transport mechanism of K+ and Na+ ions through the membranes discussed by considering ionic and hydrated radius, hydration potential, hydration free energy, entropy of hydration, and the Jones-Dole coefficient. Optimal performance was achieved for PVC-0.5%wt CNF membrane.