Surface modification of polyvinylchloride based heterogeneous cation exchange membrane was performed by graft polymerization of PAA and PAA-co-PANI/MWCNTs nanoparticles. The ion exchange membranes were prepared by solution casting technique. Spectra analysis confirmed graft polymerization clearly. SEM images illustrated that graft polymerization covers the membranes by simple gel network entanglement. The membrane water content was decreased by graft polymerization of PAA-co-PANI/MWCNTs nanoparticles on membrane surface. Membrane transport number and selectivity declined initially by PAA graft polymerization and then began to increase by utilizing of composite nanoparticles in modifier solution. The sodium and barium flux was improved sharply by PAA and PAAco- 0.01%wt PANI/MWCNTs graft polymerization on membrane surface and then decreased again by more increase of PANI/MWCNTs nanoparticles content ratio in modifier solution. The electrodialysis experiment results in laboratory scale showed higher dialytic rate in heavy metals removal for grafted-PAA and grafted-PAA-co-PANI/MWCNTs modified membrane compared to pristine one. Membrane areal electrical resistance was also decreased by introducing graft polymerization of PAA and PAA-co-PANI/MWCNTs NPs on membrane surface.