Red mud is a kind of solid waste produced during alumina extraction from bauxite. To extraction valuable iron from red mud, the technology of adding sodium sulfate-segregation roasting-magnetic separation to treat red mud was developed. During the paper, the effects of various process parameters on the extraction of iron by segregation roasting-magnetic separation were studied, and the phase transformation behavior and microstructure of iron are explored. Repeated test results showed that magnetic concentrate (mass percent), TFe of 80.29 % and overall iron recovery of 92.08 %was obtained. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) results indicated that after the segregation roasting, the hematite was transformed into a new metal phase consisting mainly of metallic iron and magnetite. The addition of sodium sulfate during the segregation roasting can obviously improve the efficiency of segregation roasting-magnetic separation for iron extraction.