Abstract X-ray diffractometry and Mössbauer spectroscopy study of Fe 50Al 25Si 25 and Fe 50Al 25Ge 25 alloys obtained by mechanical alloying (MA) of elementary powders was carried out. Phase transformation during heating of synthesized products was studied using differential scanning calorimetry (DSC). After 2.5 h of MA monophase alloys containing bcc Fe(Al, Ge) solid solutions Fe(Al, Si) are formed. Fe(Al, Si) is partially ordered B2 type and Fe(Al, Ge) is completely disordered. DSC curves of synthesized alloys displayed the presence of exothermal peaks caused by phase transformation. The metastable Fe(Al, Si) solid solution transformed into FeAl 1− x Si x (B2) and FeSi 1− x Al x (B20) equilibrium phases. The Fe(Al, Ge) solid solution transformed into equilibrium phases through intermediate stage of Fe 6Ge 3Al 2 metastable phase formation. The Fe 6Ge 3Al 2 phase dissociated into three equilibrium phases: FeAl 1− x Ge x (B2), χ-Fe 6Ge 5 and η-Fe 13(Ge, Al) 8 (B8 2). The structure of Fe 6Ge 3Al 2 was calculated by Rietveld method, the distribution of Al and Ge in the elementary cell and its parameters were calculated. Mössbauer study showed that Fe(Al, Si) and Fe(Al, Ge) solid solutions are paramagnetic. In the equilibrium state the alloy containing Si is also paramagnetic while the alloy with Ge showed ferromagnetic properties.