ABSTRACTLithium titanium oxide (Li₄Ti₅O₁₂) spinels are promising negative electrode materials for application in energy technology. In this work, we have synthesized Li₄Ti₅O₁₂ and investigated its structure, electronic properties, and electrochemical features using several analytical spectroscopy and microscopy techniques. The equally spaced lattice fringes obtained using by the high-resolution transmission electron microscopy (HRTEM) along with electron diffraction reveal that the grown Li₄Ti₅O₁₂ is well crystallized in the spinel structure without any indication of crystallographic defects such as dislocations or misfits. The electronic structure determination using high-resolution X-ray photoelectron spectroscopy (XPS) coupled with compositional studies using energy dispersive X-ray spectrometry (EDS) indicate excellent chemical quality of the Li₄Ti₅O₁₂. Under the optimal synthetic condition, the sample delivers a discharge capacity of 161 mAh/g at C/12. The good cyclability of Li₄Ti₅O₁₂ is attributed to the small expansion (δV≈1%) of the elementary unit-cell.