The efficient materials for Li-ion battery electrodes require suitable composition, high-crystallinity and appropriate structuration. The last one is important to assure an efficient exchange of Li ions between the anode and electrolyte, thus enhancing the kinetics of electrochemical reactions. Therefore, the synthesis of well-crystallized nano-sized electrode materials exhibiting high surface area is of great interest. Herein, we explore the influence of the glycothermal synthesis variations on the structure and porosity of Li4Ti5O12. The utilized precursors and their concentration have a minor influence on crystallites size, but they could be used to control the porosity of assembled particles. The prepared Li-ion battery anode could be charged at low and high rate reaching the theoretical capacity of Li4Ti5O12. The material retains its peculiar porous structuration even after 1000 cycles at charging/discharging rate of 50C which contributes to the lack of capacity fading. Additionally, 7Li NMR is performed on one of synthesized nano-structured Li4Ti5O12 and compared with commercially available nanosized Li4Ti5O12 to understand the excellent electrochemical performance. Open image in new window Glycothermal synthesis of lithium titanate, in 1,4-butanediol leads to crystalline NPs of 4-5 nm assembled into highly porous microstructures. Such structuration assures well-developed contact area between the electrode and an electrolyte in Li-ion batteries, which facilitates exchange of Li-ions. Therefore, the material shows excellent electrochemical performances. LTO characterized by different nanostructuration is obtained by varying the synthesis conditions (precursors type and concentration, temperature and co-solvent). , Highlights Pure nanostructure Li4Ti5O12 was synthesized in varying glycothermal conditions using 1,4-butanediol as the solvent. Simple adjustment of precursors and their concentration tuned the microstructure of the material without affecting the size of crystallites which oscillated around 4 nm. Nano-scaling and proper microstructuration is an effective way to improve kinetics of electrochemical reactions due to the efficient exchange of Li ions between electrodes and electrolytes. 7Li NMR was performed on synthesized material and commercial one in order to understand the peculiar electrochemical properties of the material.Read less <