Unique hollow Fe3O4 spheres are prepared by a simple template-free solvothermal reaction. In the reaction, ethylene glycol (EG) and polyvinylpyrrolidone (PVP) serve as the reducing agent and surface stabilizer, respectively. NH4Ac plays the role of the structure-directing agent, which combines with the Ostwald ripening process, resulting in the favored formation of hollow structures. The morphologies and structures are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The hollow Fe3O4 spheres exhibit excellent cycling and rate performance as anode material for lithium-ion batteries, delivering reversible specific capacities of 870mAhg−1 even after 50 cycles at 100mAg−1 and 836mAhg−1 at 500mAg−1. The excellent electrochemical performance can be attributed to their hollow nanostructure and excellent structural stability.