Sodium-ion batteries (SIBs) have attracted lots of significant interests, arising from in regard to the development of developing a low-cost energy storage system for renewable energy. Antimony-based materials with that have high theoretical storage capacities of Na+ have become one of the most focused SIB anode materials. Among of which, Sb2O4 has a higher and thus superior Na+ storage capacity of 1227mAhg−1 compared to other antinomy-based materials. In this work, one simple solvothermal process has been developed to prepare Sb2O4/reduced graphene oxide (Sb2O4/RGO) composites with a nanostructure of Sb2O4 nanorods anchored on RGO. Sb2O4/RGO shows an obviously enhanced electrochemical performance with an initial Na+ storage capacity of 842±5mAhg−1, a rechargeable capacity of 551±5mAhg−1 at 50mAg−1 after 100 cycles and an excellent rate performance of 401±5mAhg−1 at 1Ag−1.