The hexagram and arrayed β-FeOOH nanorods were first synthesized free of surfactants through the solvent-thermal method. X-ray powder diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectrum (EDAX) and thermal gravimetric analysis (TGA) were used to characterize the as-prepared products. The TEM and FESEM images showed that hexagram β-FeOOH and arrayed rod-like β-FeOOH with an average diameter of 10–15nm and an average length of 100nm (aspect ratio is about 10) were prepared. Electrochemical tests show that these nanorods deliver a large discharge capacity of 277mAhg −1 versus Li metal at 0.1mAcm −2 (voltage at 1.5–4.2V). Treated the as-synthesized rod-like β-FeOOH by annealing, rhombus hematite was obtained.