In this work, hierarchically mesoporous TiO2 spheres were successfully fabricated. The synthesis method could be simply described as adding Ti(SO4)(2) into the disperse phase of a conventional emulsion polymerization where emulgator was discovered to play an important role in the formation of the ingenious structure. When used as anode materials for lithium-ion batteries, it delivered a high capacity of 192 mA h g(-1) at 0.2 A g(-1) with the retention of 94.3% after 100 cycles, and a reversible capacity of 114 mA h g(-1) could be kept at 2 A g(-1) after 2000 cycles. At the same time, an excellent initial Coulombic efficiency (> 90%) and satisfactory rate performance were obtained.