Metallic Fe (hereinafter abbreviated as M.Fe) is suspended in steelmaking slags due to the stirring action during blowing and is mainly recovered via pulverization, classification, and magnetic separation. However, steelmaking slags are hard, and it is difficult to transform irregular-shaped and fine M.Fe in slags into free particles through the conventional pulverization method, which requires a large energy consumption. In this study, pulverization and separation experiments of steelmaking slags were performed using electrical pulse disintegration, which is completely different from the conventional pulverization method and capable of causing preferential fracture at the heterophase interface. As a result, several free particles of M.Fe with almost no slag attached were obtained from the coarse and fine pulverized particles. In addition, the electric field analysis results of a system where spherical M.Fe exists in a slag show that electric field concentration occurs in the front and back directions of the external magnetic field. The findings also show that a fracture can occur at the interface between the M.Fe and slag due to the combination of increased discharge probability, concentration of thermal energy, and generation of the Maxwell stress. Furthermore, the larger the pulverized mass, the higher the pulverization efficiency. In sum, electrical pulse disintegration may be advantageous for actual operations, where large quantities of oxides employed in the steel industry, such as steelmaking slag, spent refractories, and raw materials, should be treated in a short time with low energy consumption.