X-ray diffraction and Mössbauer spectroscopy were used to study the structure and hyperfine interactions in Fe80Mo20 and Fe50Mo50 prepared by mechanical alloying. Two solid solutions, i.e. Fe(Mo) and Mo(Fe) with b.c.c. lattice were formed during milling of Fe80Mo20. Mössbauer spectra revealed different magnetic arrangements in these solid solutions. In the case of Fe50Mo50 no amorphisation was observed, as literature data suggest. During mechanosynthesis of Fe50Mo50 a paramagnetic Mo(Fe) solid solution was probably formed. © 2002 Elsevier Science B.V. All rights reserved.