Octahedral-like Li0.5Fe2.5O4 crystallites have been fabricated using a TEA-assisted route under mild conditions. The as-prepared powders were characterized in detail by conventional techniques such as XRD, TEM, and FESEM. The saturation magnetization (Ms), remnant magnetization (Mr), and coercivity (Hc) have been determined to be 84, 6 emu/g, and 85 Oe, respectively. Meanwhile, the electrochemical properties of Li0.5Fe2.5O4 demonstrate that it delivers a large discharge capacity, which might find possible application as an electrode material in lithium cells.