TiO2/carbon hollow spheres (TiO2/C-HSs) have been successfully prepared using a template method. During the synthesis procedures, SiO2 spheres were used as template, titanium tert-butoxide and dopamine were used as TiO2 and carbon precursor, respectively. The TiO2/C-HSs were characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption measurements, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetry (TGA) measurements, and raman spectra analysis. When utilized as anode materials for sodium-ion batteries, the TiO2/C-HSs anode can deliver a high specific capacity and remarkable rate performance. The excellent electrochemical performance of TiO2/C-HSs can be ascribed to the hollow sphere structure, the existence of carbon and the large surface area and porous structure.