• Submicro-sized Li 4 Ti 5 O 12 was prepared by simple citric-nitrate combustion method. • Li 4 Ti 5 O 12 powder displays good cycling performance and excellent rate-capability. • Li 4 Ti 5 O 12 exhibits a superior high temperature cycling performance. • The preparation process is mild and scalable. Single phase Li 4 Ti 5 O 12 powder with porous particle structure is synthesized via a simple, mild and productive citric-acid combustion method. The Li 4 Ti 5 O 12 particle is composed of submicro-scaled grains with size of 100–200 nm. The synthesized Li 4 Ti 5 O 12 shows high reversible capacity (ca. 165 mAh g −1 at 0.5 C), excellent rate-capability (ca. 115 and 100 mAh g −1 at 10 and 20 C, respectively) and high temperature cycling stability (50 °C). Under expanded cut-off voltage range of 0.01–2.5 V, it delivers a high specific capacity of ca. 230 and 170 mAh g −1 at 0.5 and 10 C, respectively, while maintaining an excellent cycling stability. The synthesized Li 4 Ti 5 O 12 shows fast de-lithiation but slow lithiation kinetic processes. When discharged at constant 1 C while charged at 10, 20 and 30 C, respectively, the specific capacity of 162, 160 and 158 mAh g −1 can be achieved. The excellent electrochemical performance of the combustion synthesized Li 4 Ti 5 O 12 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.