Spinel lithium titanate (Li4Ti5O12) has attracted extensive attention by virtue of its inherent features of zero strain and high operating potential, which results in outstanding structural stability and remarkable safety as anode materials for lithium-ion batteries. But, there are two issues of low specific capacity and poor electrical conductivity yet need to be satisfactorily solved before the practical application of Li4Ti5O12 anode can be well achieved in lithium-ion batteries. Herein, a novel hierarchical structure of clew-like microparticles constructed by ultrafine Li4Ti5O12 nanowires has been successfully prepared via a facile approach. The combination effect of ultrafine nanowire unites and non-compact clew-like architecture provides the as-prepared Li4Ti5O12 with excellent electrochemical performance. A high reversible specific capacity of 184.1 mAh g−1 can be obtained at 20 mA g−1 after 400 cycles. What is more, a capacity of 177.8 and 152.2 mAh g−1 can be gained even after 2500 cycles respectively at 200 and 4000 mA g−1, exhibiting high capacity, superior rate property and outstanding cycling stability. This work may open up a broader vision into developing nanostructure Li4Ti5O12 anode materials for advanced lithium-ion batteries.