Hierarchical mesoporous nest-like Li4Ti5O12 is prepared by a hydrothermal reaction, using CTAB as the surfactant, and water-soluble titanium complex [NH4 +]4[H+]2[Ti4(C2H2O3)4(C2H3O3)2(O2)4O2]6− as the titanium precursor. As-prepared Li4Ti5O12 has a tiny crystallite size of 8.2nm and a very large surface area of 219.2m2 g−1. Commercial micrometer-sized Li4Ti5O12 is also tested for comparision, and up to 10000mAg−1 (57C) is applied to evaluate these two samples as the anode material for lithium ion batteries. Our products deliver much better cycling and rate performances, especially at high current densities. 135.1mAhg−1 is obtained after 200 cycles at 2500mAg−1, and 113.6mAhg−1 is obtained at 10000mAg−1. The polarization in our products is much lower, and our products also show higher lithium diffusion coefficient and higher exchange current density, calculated from CV and EIS measurements.