In this study, we report a higher electrochemical performances of Li4Ti5O12 (LTO) anode material via solid method, then adding different contents of Fe2O3 into LTO (FxLTO, x = 0.1, 0.2, 0.3, 0.4) secondary calcined. The study shows that pure LTO holds the highest electrochemical performances at 750 °C. Additionally, F0.2LTO demonstrates an outstanding discharge capacity of 251.9 mAh g−1 at 20 mA g−1 for lithium ion batteries; even cycled at 100 mA g−1 for 100 times, a capacity of 192.1 mAh g−1 retains. Particularly, the specific capacitance of Fe0.2LTO, with higher surface area of 28.4937 m2 g−1 and pore volume of 0.4187 ml g−1, reaches 65.17, 46.56, 26.71, 19.32 F g−1 at 50, 100, 500, 1000 mA g−1 for hybrid capacitors, respectively. Even cycled at 50 mA g−1 for 500 times, a capacitance of 20.18 F g−1 retains. Obviously, Fe0.2LTO demonstrates the remarkable electrochemical performances than LTO for lithium ion batteries and hybrid capacitors. Therefore, Fe-doping LTO has enhanced electrochemical performance as anode material for energy storage device.