The surface segregation of a Fe 94 Si 6 and Fe 76 Si 24 alloys was studied using high resolution photoemission spectroscopy with synchrotron radiation at 150-166 eV photon beam energy. During Ar + ion sputtering and following heat treatment, a SiO 2 layer and segregation of Si atoms in three clearly resolved phases occurred. This indicates formation of silicides, mainly Fe 3 Si and cubic FeSi superstructures. The photoemission measurements were complemented by 57 Fe Mossbauer spectroscopy in different modes which gave information about deeper surface layers (approximately 10-30000 nm) of the samples. The results derived from the Mossbauer spectra support the conclusions concerning phase composition of the surface deduced from photoemission spectroscopy.