The utilization of nickel slag has attracted much attention due to its high-content of valuable elements. As a part of these efforts, this work focuses on whether magnetite crystals, obtained from nickel slag via molten oxidation, magnetic separation, and ball-milling can be used as a microwave absorber. The composition,morphology,microstructure,magneticproperties, andmicrowave absorption performance were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), and vector network analysis (VNA). The results reveal that the magnetite crystals exhibit excellent microwave absorption properties because of the synergistic action between dielectric loss and magnetic loss. The minimum reflection loss (RL) of the particles obtained after 6 h ball-milling reaches -34.0 dB at 16.72 GHz with thickness of 5 mm. The effective frequency bandwidth (RL ≤ -10 dB) is 4.8-5.4 GHz and 15.9-17.6 GHz. Interfacial polarization of the particles could play a crucial role in improving absorbing properties because several components contained in the particles can dissipate electromagnetic wave effectively. The current study could show great potential in the preparation of magnetite crystals and utilization of nickel slag. © 2020 by the authors.