The decomposition of goethite and goethite/siderite concentrates into hematite with thermal modification was studied through the measurements of X-ray diffraction (XRD), scanning electronic microscope (SEM) and thermal gravimetric analysis (TGA). The experimental results showed that goethite decomposed into hematite directly at around 300°C without any intermediate phase and the decomposition of siderite completed at 500°C. Nanoscale granular structures were observed in the thermally treated products. It deserves highlighting that the decomposition processes proceeded from surfaces into bulks.