Single phase Li4Ti5O12 powder with porous particle structure is synthesized via a simple, mild and productive citric-acid combustion method. The Li4Ti5O12 particle is composed of submicro-scaled grains with size of 100–200nm. The synthesized Li4Ti5O12 shows high reversible capacity (ca. 165mAhg−1 at 0.5C), excellent rate-capability (ca. 115 and 100mAhg−1 at 10 and 20C, respectively) and high temperature cycling stability (50°C). Under expanded cut-off voltage range of 0.01–2.5V, it delivers a high specific capacity of ca. 230 and 170mAhg−1 at 0.5 and 10C, respectively, while maintaining an excellent cycling stability. The synthesized Li4Ti5O12 shows fast de-lithiation but slow lithiation kinetic processes. When discharged at constant 1C while charged at 10, 20 and 30C, respectively, the specific capacity of 162, 160 and 158mAhg−1 can be achieved. The excellent electrochemical performance of the combustion synthesized Li4Ti5O12 is ascribed to the porous particle structure and small grain size feature, which ensure the good contact with electrolyte and reduce the lithium ion/electron diffusion distance, and therefore enhance the electrode reaction process.