Integrated design of both porous structure and crystalline morphology is expected to open up the way to a new class of materials. This report dem- onstrates new nanostructured Li4Ti5O12 materials with hierarchically porous structures and ?ower-like morphologies. Electrochemical studies of the electrodes of Li-ion and Na-ion batteries clearly reveal the advantage of nano- architectural design of active materials. In addition, the temperature depend- ence of Na + -insertion/extraction capacity in relation to Li4Ti5O12 electrodes is for the ?rst time evaluated and it is found that elevation of the cell operating temperature effectively improves the rate capability of the Na-ion batteries. Based on the new ?ndings, it is suggested that specially designed Li4Ti5O12 materials allow for high-performance Na-ion batteries that are available as large-scale storage devices for applications such as automotive and stationary energy storage.