||Deionization of salt, contaminated underground and inorganic waste waters for water recycling and reuse is of increasing importance mainly due to the shortage of freshwater worldwide. Membrane capacitive deionization (MCDI) possessing a high electrosorption capacity and energy efficiency has been considered a promising method for desalination. However, the MCDI reaction system has limited applications because of the high interfacial resistance during operation. In the present work, the novel sulfonated graphene oxide (SGO) serving as a hydrophilic cation exchange membrane that was coated directly on the activated carbon (AC) electrode was prepared to enhance capacitive deionization of saltwater. Experimentally, the electrosorption capacity and charge efficiency of the AC/SGO (negative)||AC (positive) electrode pair using the coated SGO thin film increased from 12.8 to 19.8 mg/g and 56.7 to 89.3%, respectively. The enhancements were associated with the reduction of the co-ion effect during electrosorption. The strong negative PhSO3- group grafted on the SGO thin film could selectively accelerate the transport rate of cations during CDI. The increase of the charge efficiency also led to lower implemented current. This work demonstrates a simple, low-cost and effective desalination method that will likely have many new applications especially in water recycling and reuse.