The effect of composition and casting temperature on the microstructure and the oxidation state of Fe in a series of glass/glass ceramic materials that contain Fe 2 O 3 , PbO, Na 2 O and SiO 2 is studied by means of X-ray fluorescence mapping (XRF), micro-(l-) and conventional X-ray absorption fine structure (XAFS) and 75 Fe Mo Β¨ssbauer spectroscopies. The Mo Β¨ssbauer results reveal that the majority of Fe exists in the Fe 3+ state. Divalent Fe is detected only in small amounts (2.1-5.7 at.%) in the ternary samples consisting of Fe 2 O 3 , SiO 2 and Na 2 O. The XRF mapping demonstrates that the ternary samples Fe 2 O 3 -Na 2 O-SiO 2 that contain more than 40 wt.% of Fe 2 O 3 develop Fe-rich islands. According to the combined l-EXAFS and EXAFS results, 44 wt.% of the Fe atoms belong to those Fe-rich microcrystalline islands, where they are octahedrally coordinated, while the rest belong to the vitreous matrix where they are tetrahedrally coordinated. The Fe-O distance is found equal to 0.188 nm and 0.193 nm in the vitreous and microcrystalline regions, respectively. The differences in the NEXAFS spectra, due to the different local environment of Fe embedded in the vitreous or microcrystalline regions, are also discussed.