We have studied the formation of metal-metalloid alloys for Fe-Si and Fe-C as a function of milling times. These alloys were produced using mechanical alloying. The effect of milling time on local structural changes of Fe-Si and Fe-C has been investigated by means of Mossbauer spectrometry, EXAFS study and XRD. Saturation magnetization was also measured by VSM. XRD pattern from mechanically alloyed Fe-Si and Fe-C powders indicates the formation of solid solution. The different variation of lattice parameters could be analysed from the different substitution of Si and C atoms into the Fe structure. The Mossbauer spectrum showed typical sextets in the 1 h milled sample corresponding to alpha-Fe spectrum. Increasing the milling time, the sextets became broader due to appearance of disordered Fe atoms in both solid solutions. The hyperfine field distributions were decreased as increasing milling time, which is similar trend with magnetization distribution. (C) 2004 Kluwer Academic Publishers.