Coral-like α-Fe2O3 nanostructures modified by surfactant CTAB have been successfully obtained via a solvothermal process by using FeCl3 6H2O and oxalic acid as the starting materials. The coral-like α-Fe2O3 nanostructures with good-crystalline consist of well-aligned α-Fe2O3 nanoflakes with an average thickness of about 40 nm growing radially from the center of the nanostructures. The obtained products are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), superconducting quantum interference device magnetometer (SQUID). Magnetic hysteresis measurements indicate that coral-like α-Fe2O3 superstructures show a normal ferromagnetic behavior with the remanence and coercivity of 0.2346emu/g and 1862Oe at room temperature. CTAB, the reaction temperature and solvent played an important role in controlling the final morphology of the products.