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.