Geompolymers and their engineering applications have attracted significant attention of the scientific community. This is due to properties such as good thermal stability and high resistance to aggressive environments. Most studies on this subject are based on traditional precursor materials such as calcined kaolinite clay (metakaolinite) and fly ash. The iron content is significant, reaching around 10% in metakaolinite, for instance. The role of iron in geopolymers still lacks systematic investigation. This can be attributed to the limitations presenting nuclear magnetic resonance (NMR) spectroscopy, which is a widely used technique to study geopolymers structure. Ferromagnetic elements such as iron, which is often present in some precursors, affect the magnetic response of the material, compromising the proper analysis of its structure by NMR results. Iron content in some industrial residues may be several times higher as it is often found in metakaolinite. This work presents x-ray diffraction, infrared and Mössbauer spectroscopy studies on the distribution of iron species in iron oxide/hydroxide-rich precursor, which was used to synthesized geopolymers.