A carbon-coated composite consisting of Sn, SnO2, and porous carbon-nanofiber membrane (SnSnO2CNF@C) was successfully prepared via electrospinning followed by carbonization and low-temperature hydrothermal treatment. The thickness of the carbon overlayer formed by using sucrose as the carbon source could be well controlled by adjusting the sucrose concentration. The three-dimensional (3D) nanofiber network structure allowed the SnSnO2CNF@C membrane to be used directly as an anode in lithium-ion batteries without adding any polymer binders or electrical conductors. The composite electrodes of this material exhibited a high discharge capacity of 712.2mAhg1 at a high current density of 0.8Ag1 after 200 cycles, as well as good cycling stability and excellent rate capability, which can be ascribed to the improved electrochemical properties of the SnSnO2 particles provided by the protective carbon coating and the 3D carbon nanofiber membrane. The composite can thus be widely used as an advanced binder-free anode material in high-current rechargeable lithium-ion batteries and extended to the fabrication of flexible electrodes.