Porous Li4Ti5O12 nanoclusters with high surface area are synthesized by a facile solution-based method followed by low-temperature calcination. The Li4Ti5O12 nanoclusters present the key characteristics needed to serve as high-performance negative electrodes for lithium ion batteries, including nano-sized dimension of the Li4Ti5O12 clusters (50–100 nm) for short ion and electron transfer path, and high surface area (142 m2 g−1) with mesoporosity (pore diameter 2–6 nm) for easy access to the electrolyte and efficient ion transport. Based on these characteristics, the Li4Ti5O12 electrode delivers an initial capacity of 173 mAh g−1 at the rate of 0.5 C, comparable to its theoretical capacity. Excellent cycling stability at high rates is achieved in the Li4Ti5O12 electrode, offering potential to serve as a negative electrode material for high rate lithium ion battery applications.