We report the preparation of an electrostatically-coupled graphene oxide nanocomposite cation exchange membrane (CEM) based on sulfonic group containing graphene oxide (SGO) (45 wt % loading) and polyvinylidene fluoride (PVDF), where the ion exchange groups were provided by the SGO additive. SGO was prepared via the mixing of graphene oxide (GO) with a mixture derived from 3,4-dihydroxy-L-phenylalanine (L-DOPA) and poly(sodium 4-styrenesulfonate) (PSS). A mold-casting technique was developed to fabricate the free-standing nanocomposite CEM. The presence of sulfonic groups in the nanocomposite was confirmed with FTIR spectroscopy. Energy dispersive spectroscopy analysis showed the SGO was distributed across the entire membrane matrix, with minimal aggregation. The resultant SGO/PVDF nanocomposite CEM membrane demonstrated high hydrophilicity and high water uptake, but low swelling ratio. Furthermore, evaluation of the electrochemical properties of the nanocomposite CEM showed favorable ion exchange capacity (0.63 ± 0.08 meq/g), permselectivity (0.95 ± 0.04), and area resistance (2.8 ± 0.2 Ω cm2). The nanocomposite CEM show good potential for use in electromembrane desalination applications.