Using lithium acetate dihydrate and tetra-n-butyl titanate as the raw materials, spinel Li4Ti5O12 was successfully synthesized by a modified rheological phase method. Thermogravimetric analysis and differential scanning calorimetry (TG–DSC) of the thermal decomposition process of the precursor and X-ray diffraction (XRD) data indicate the crystallization of lithium titanates has occurred at 580°C, and main phase Li4Ti5O12 has obtained at 600°C. Laser granulometer and scanning electron microscope (SEM) have been employed to estimate the particle size distribution, morphology and microstructure of the products. It reveals the prepared Li4Ti5O12 powder had a small particle size (about 140nm) and narrow size distribution (d 0.1 =0.07, d 0.5 =0.139, d 0.9 =2.813μm). Galvanostatic charge and discharge tests were carried out to characterize the electrochemical performances of Li4Ti5O12. The result indicates that the Li4Ti5O12 electrode material obtained from the precursor that had been experienced heat treatment at 110°C exhibited discharge capacities of 161.6, 156.5 and 112.3mAhg−1 after 50 cycles at current rates 1, 2.5 and 10C, respectively, demonstrating excellent high rate performance, due to the pure and well crystallized Li4Ti5O12 with ultrafine particles and narrow size distribution.