An experimental analysis of structural and magnetic properties for the system of FexMn0.912—xAl0.075C0.01Cu0.003 alloys with 0.50 ≤ x ≤ 0.80 is presented. These alloys were obtained by mechanical alloying in a planetary milling machine using 22 h of milling time. By X-ray diffractions (XRD) it is shown that alloys with a percentage between 50 and 75 at% of Fe exhibit a f.c.c. phase, while for alloys with 80 at% Fe there is a coexistence of f.c.c. and b.c.c. phases. It is also shown that the grain size does not change noticeably with Fe content increase. Using M�ssbauer spectroscopy an antiferromagnetic behaviour is found, which is typical of f.c.c. phase and it tends to a paramagnetic one with Fe content increase. For the 80 at% Fe alloy, the coexistence of ferromagnetic (typical of b.c.c. phase) and antiferromagnetic phases is obtained. An increase of the isomer shifts (IS) parameter with an increase of the Fe concentration was obtained.