In this study, ternary Cu2SnS3 (CTS) nanostructure materials with high crystallinity were successfully prepared via a facile solvothermal method, which was followed by high-temperature treatment. The morphology of the as-synthesized samples is uniform flower-like spheres, with these spheres consisting of hierarchical nanosheets and possessing network features. Sodium storage measurements demonstrate that the annealed CTS electrodes have high initial reversible capacity (447.7 mAh·g−1 at a current density of 100 mA·g−1), good capacity retention (200.6 mAh·g−1 after 50 cycles at a current density of 100 mA·g−1) and considerable rate capability because of their high crystallinity and unique morphology. Such good performances indicate that the high crystallinity CTS is a promising anode material for sodium ion batteries.