The magnetic and structural properties of the FexMn0.95–xAl0.05 system (0.40 < x < 0.80) were analyzed by X-ray diffraction and Mössbauer spectroscopy techniques. The samples were prepared by mechanical alloying during 12, 24, 36 and 48 hours. The X-ray patterns show a FCC type structural phase. The lattice parameter slightly decreases when iron concentration increases. The grain size shows a growing tendency between 12 and 24 h. Afterwards, a decreasing behavior for 36 h and it stabilizes for 48 h. The Mössbauer spectra present an antiferromagnetic peak; however, the magnetic phase shows a shifting through the paramagnetic state when the Fe-concentration grows. The Mean Hyperfine Field (MHF) decreases as Fe concentration increases. Despite the differences between our preparation method and that provided by the arc melting technique, the final results present good agreement among them. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)