Membrane capacitive deionization (MCDI) featuring both high electrosorption capacity and high energy effi ciency holds promise for desalination. However, the large-scale applications of MCDI are limited greatly by the high cost of commercial ion-exchange membranes and the interfacial resistance. Here, a new strategy for high-performance MCDI is established using sulfonated graphene (SG) as cation-selective coating. A continuous ultrathin SG coating via self-assembly is formed and attached tightly onto the surface of electrospun carbon nanofi bers (CNFs) by a simple yet effective dip-coating technique, yielding SG-CNF composites with a hydrophilic surface, high electrochemical specifi c capacitance, and greatly reduced interfacial charge transfer rate. These result in signifi cantly enhanced capacitive deionization performance in terms of both electrosorption capacity and charge effi ciency. The SG coating shows excellent cation selectivity for an asymmetric cell with SG-CNFs as a cathode. The new approach may pave a way to novel micro-MCDI, i.e. novel applications of functional graphene-based materials for highperformance, energy-effi cient, and cost-effective desalination.Adv. Mater. Interfaces 2015, 2, 1500372 www.advmatinterfaces.de www.MaterialsViews.com Adv. Mater . Interfaces 2015, 2, 1500372 www.advmatinterfaces.de www.MaterialsViews.com Scheme 1. a) Schematic of the three-step synthesis of SG; insets display the digital images of rGO and SG suspension after standing for 1 week. b) Schematic of the "dip-coating" process; insets show the digital images of rGO-CNFs and SG-CNFs.