Uniform 3D rod‐like α‐Fe2O3 nanostructures are prepared by a simple ultrasonic‐assisted hydrolysis precipitation method. The obtained α‐Fe2O3 samples are characterized by X‐ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), and electrochemical workstation. These rod‐like α‐Fe2O3 nanostructures, with a mean diameter of about 38 nm, their ratios of length to diameter are about 5–8. The interfacial electron transfer properties of rod‐like α‐Fe2O3 nanostructures are verified. The current synthetic strategy provides a convenient, low‐cost, and nontoxic route to prepare 3D architectures of other semiconductors, and it is important for exploring oxide‐based nanostructures.