The effect of the gel-drying temperature, annealing time at 900°C and calcination temperature used in the sol–gel synthesis of Li4Ti5O12 spinel (LTO) on the purity phase, structural and morphological features, and electrochemical properties has been investigated. Synthesized LTO-samples have been characterized by X-ray diffraction and scanning electron microscopy (FE-SEM). High purity LTO-spinels have been synthesized by adjusting the thermal treatment conditions. The rate capability and cycleability of the LTO-samples have been studied by galvanostatic techniques in Li-half cells. The influence of the gel-drying temperature on the LTO-phase purity has been clearly evidenced. Both annealing time and calcination temperature notably modify the morphological features as the particle size, the agglomeration of the particles and its porosity. All the studied LTO-samples show a similar evolution of the capacity vs current in the rate capability test. Cycling studies have shown that LTO-samples exhibit high reversibility. Among the sol–gel synthesized LTO-spinels that prepared after drying the gel precursor at 150°C, and then annealed at 550°C for 6h and 900°C for 1h shows the best electrochemical performances. It nominal capacity is 165mAh/g and it has a reversible capacity of 87mAh/g at 1C (175mA/g) with no capacity fading after 100 cycles.