The thermal annealing effect on the morphological, structural and electrochemical properties of hydrothermal synthesized Li4Ti5O12 / TiO2 has been studied. Lithium titanate (Li4Ti5O12) nanopowders are successfully synthesized by hydrothermal method using titanuim tetrabutyl and lithium hydroxide followed by thermal annealing process at different temperatures: 500°C, 800°C and 900°C.The X-ray diffraction (XRD) patterns indicates the appearance of the Li4Ti5O12 phase at a temperature above 800°C formed after the reaction of the two phases: TiO2 and Li2TiO3 which appear at 500°C. Though, the prepared electrode by the powder annealed at 800 °C shows an initial capacity of about 173.1 mAh/g (0.1 C), which retained at 75.6 mA h/g after 100 cycles.