Single-crystalline Li4Ti5O12 nanorods have been successfully prepared through a molten salt method, followed by a precipitation method, and characterized with X-ray powder diffractometry, field-emission scanning electron microscopy, and transmission electron microscope. Their electrochemical properties have been studied by charge/discharge cycling and cyclic voltammetry. The results show that the single-crystalline Li4Ti5O12 nanorods reveal high capacity, excellent rate capability and cycle stability. The discharge capacity up to 176.4 mAh g−1 at 0.1 C rate is achieved. When tested at 10 C rate, the first discharge capacity reaches 135.9 mAh g−1, and the capacity retention is more than 61.5% after 1500 cycles. Furthermore, high rate capability Li4Ti5O12/LiMn2O4 full cells have been made using Li4Ti5O12 nanorods as the negative electrode, which display superior cycle stability at high rate. The discharge capacity and the mass energy density sequentially reach 40 mAh g−1 and 86.4 Wh kg−1 at 10 C rate, while the capacity retention is about 60% after 1000 cycles.