Hollow urchin-like SnO2 nanospheres with ultrathin nanorods have been successfully synthesized via a simple complex solvothermal route. The formation mechanism of the as-synthesized SnO2 nanospheres was simply explained. When tested as anode, the as-obtained hollow urchin-like SnO2 nanospheres exhibit excellent rate and cycling performances. It was expected that the as-synthesized SnO2 nanospheres could be applied as anode materials for future lithium-ion batteries.