Fe(Ni, Si) solid solutions were elaborated by high energy mechanical alloying from elemental Fe, Ni and Si powdersfor a milling time of 72 h. From X-ray diffraction (XRD) analysis, it has been shown that the Fe(Ni, Si) samples present a single phase in the whole range of Si content and exhibit a solid solution of disordered bcc α-Fe. The lattice parameter a (Å) of the new structures and the mean crystallitessize <D> (nm) were found to decrease with increasing Si contents. In contrast, the microstrain behaviour presents two different stages as the Si contents are increased. Scanning Electron Microscopy (SEM) images confirmed the behaviour of the mean crystallites size, where it can be seen that the addition of Si promotes the reduction of the size of powder particles. The saturation magnetization Ms was found to decrease by a factor of almost 1.4 and the coercively was found to increase by a factor of almost 2.4, when the Si content was increased from x= 0 % to x= 20 %. The Mössbauer spectroscopy confirmed the local in site crystal locations of Si and Ni as they diffuse into the matrix of the bcc α-Fe structure to form a solid solution.