Nanostructured (Fe0.6Al0.4)100-xSix powders with x= 0, 5, 10, 15 and 20 at.% were elaborated by means of mechanical alloying for a fixed milling time of 72 h. We have investigated the effect of silicon addition on the microstructure and magnetic properties of these ternary alloys. X-ray diffraction experiments reveal that these powders are single-phase disordered solid solutions with body centered cubic crystal structure. The lattice parameter diminishesalmost linearly as the Si content increases. The mean crystallite size,<D(nm)>, is around three times smaller for the samples with higher amount of Si (≈ 10 nm) compared with that of the binary alloy (27 nm). Moreover, the volume fraction of grain boundaries (fgb) seems to be higher with increasing the Si content, as well as both dislocation density (ρ) and lattice microstrain (<ε>),that follow alinear trend. The SEM images show that the Si helps in refining the shape and size of the powder particles, leading to a nearly homogeneous small particles.The addition of Si strongly affects the value of the saturation magnetization, Ms, that falls nearly an order of magnitude for the sample with 20 at.% Si, while the coercivity remains almost unchanged. The Mössbauer spectra show the presence of a sextet (ferromagnetic phase) and a singlet or a doublet (non ferromagnetic phase), except for the sample corresponding to x = 10, where only one singlet is observed in the spectrum.