Nanostructured Li4Ti5O12 (spinel) was prepared via a method employing lithium ethoxide and Ti(IV) alkoxides as the starting reagents. The optimized materials contained less than 1% of anatase as the main impurity and, depending on the synthetic conditions, they exhibited the BET surface areas of 5-183 m<2>/g. Trace amount of anatase in Li4Ti5O12 was conveniently determined by cyclic voltammetry of Li-insertion. Thin-film electrodes from nanostructured Li4Ti5O12 spinel exhibit excellent activity towards Li-insertion, even at charging rates as high as 250C. This behavior compares favorably with that of microcrystalline Li4Ti5O12 made by conventional high-temperature solid-state synthesis. A use of this compound in lithium secondary batteries is also disclosed.