Nano-sized spinel Li4Ti5O12 powders were synthesized by a sol–gel process. The cubic spinel structure without impurity phase of the synthesized Li4Ti5O12 powders was confirmed by X-ray diffraction. The average grain size of the synthesized powders was found to be around 39nm. In situ X-ray absorption spectroscopy (XAS) has been performed on the Li4Ti5O12 electrode to investigate its change in the oxidation state and the local environment of the electrode during charging and discharging processes. The X-ray absorption near edge spectroscopy (XANES) analysis showed that the absorption edge energy shifts towards lower and higher energy, respectively, during discharge and charge processes, indicating the reversibility of the electrode is quite good. It was worthy to note that the discharging capacity and the charging capacity obtained for the nano-sized Li4Ti5O12 electrode in the potential range of 0.01–1.75V are 255 and 242mAhg−1, respectively. However, the specific charge capacity obtained in the potential range of 1.0–2.0V is 126mAhg−1. The spinel Li4Ti5O12 electrode maintains the cubic spinel structure for repeated cycling resulting in good cyclability and the capacity retention.