In this research, new smart nanofibers are prepared and used to fabricate of cation exchange membranes (CEMs). In this way, poly acrylic acid (AA)-grafted-poly (vinylidene fluoride) (PAA-g-PVDF) nanofibers including ethylene glycol-octaglycidyloxypropyl-silsesquioxane (EG-POSS) nanoparticles, were fabricated by electrospinning on the polyvinylchloride-co-Resin (PVC-co-Resin) membranes as substrate. Moreover, nanogels with dual pH/redox responsive properties were synthesized by the precipitation polymerization of methacrylated dextran (DEXMA), acrylamide, and N, N′-bis (acryloyl) cystamine (BAC) as a redox-responsive cross-linker. The synthesized nanogels were used to the surface modification of produced membranes. The synthesized nanogels and membranes were analyzed by Fourier transforms infrared (FTIR) analysis, field emission scanning electron microscopy (FESEM), scanning optical microscopy (SOM), X-Ray diffraction analysis (XRD), dynamic light scattering (DLS) and Brunauer-Emmet-Teller (BET). The membrane properties such as specific water content, dialytic rate, ionic permeability, permselectivity, electrical resistance, and energy consumption were examined. Membranes had highly sensitive responsiveness to different salts and at various pH. The results indicated the improvement of ion exchange capacity, ionic permeability, water content and flux for modified membranes. The modified membrane also showed significant separation capacity for Cu2+, Cr2+, and Mg2+ removal from water. Also fabricated membranes exhibited higher dialytic rate in copper ions removal than chromium ions.