Na-ion battery is playing an important role as a low-cost alternative power source to Li-ion battery. Developing novel carbonaceous anode materials is highly demanded for high performance and environmental benignity. We report, for the first time, the graphene sheets covalently bonded with sulfur atoms as Na-ion battery anode material with a large reversible capacity of 291mAhg−1 and an outstanding rate capability with 127 and 83mAhg−1 at 2.0 and 5.0Ag−1 (charging/discharging in 3.8 and 1min, respectively), and a long cycling stability as well. Both experiment and density functional theory calculation proves that the superior performance is mainly attributed to the unique nanoporous structure stemmed from the chemically S doping. This material holds great promise in future application of low cost, high-performance Na-ion batteries.