Self-supported Li4Ti5O12 nanowire arrays with high conductivity architectures are designed and fabricated for application in a Li-ion battery. The Li4Ti5O12 nanowire arrays grow directly on Ti foil by a facile solution-based method, further enhancing Li-ion storage properties by creating Ti3+ sites through hydrogenation. This configuration ensures that every Li4Ti5O12 nanowire participates in the fast electrochemical reaction, enabling remarkable rate performance and a long cycle life.