X-ray photoelectron spectroscopy was used to obtain information on local atomic arrangements and electronic structure in Y 2 O 3 –Al 2 O 3 –SiO 2 glass system doped with up to 1mol% Fe 2 O 3 . Core level photoelectron peaks of Si2p, Al2p and O1s in glasses are symmetric and can be fitted to a single peak, suggesting that there is one kind of site for these elements. Most of the oxygen atoms in the different configurations are of bridging type and, therefore, the contributions to the O1s core level spectrum from these configurations are undistinguishable. The photopeak symmetry and the binding energies of O1s electrons show these glasses to be covalent compounds. EPR results indicate that the irons are located in sites subjected to different crystalline field strengths.