Electrochemical performance, abundance and cost are three crucial criteria to comprehensively evaluate the feasibility of Li4Ti5O12 as an electrode material for lithium-ion batteries (LIBs). Herein, hierarchical hollow Li4Ti5O12 microspheres (HLTOMs) assembled by zigzag-like nanosheets are synthesized by hydrothermal treatment of scalable lithium peroxotitanate complex solution using low-cost commercial H2TiO3 particles as titanium sources, followed by a calcination treatment. Precursor solution concentration, Li/Ti ratio, hydrothermal temperature and duration are found correlative and should be optimized to obtain pure Li4Ti5O12 products. A high yield of HLTOMs up to 120 g L−1 was achieved. Due to the unique morphology, the HLTOMs deliver an outstanding rate capability of 139, 125 and 108 mA h g−1 at 10, 20 and 30 C, respectively, and exhibit 94% capacity retention after 1000 cycles at 30C indicating excellent stability. These values are much superior to those of commercial Li4Ti5O12 particles (CLTOPs), showing HLTOMs are promising anode materials for LIBs.