Sn/SnO2/C ternary composite with core-shell structures is synthesized using a hydrothermal method and subsequent heat treatment at 973 K. This Sn/SnO2/C composite exhibits the micro-sphere structure that nanosized Sn and SnO2 particles are well encapsulated in the carbon matrix. As anode for sodium-ion batteries, the composite displays superior cycling stability and rate capability to SnO2/C and Sn/C composites. It delivers a high initial discharge capacity of 1110 mAh g−1 with good cyclability. Even at a high current density of 1000 mA g−1, a reversible capacity of 120 mAh g−1 is still remained. The enhanced sodium storage performance of Sn/SnO2/C anode is attributed to the synergistic effect provided by Sn, SnO2 and unique core-shell structure. Since the deformation of Sn can increase the reversible capacity of the SnO2 electrode and the carbon matrix could act as a buffer to accommodate the volume change.