Abstract Nanostructured Fe–6 wt.%Mo powders were prepared by mechanical alloying in a high-energy planetary ball-mill. The structural changes and the kinetics of Mo dissolution were studied by using X-ray diffraction. The crystallite size reduction down to about 11 nm is accompanied by the introduction of internal strains up to 1.1% (root-mean square strain, rms). After 24 h of milling, a bcc Fe(Mo) solid solution is formed. The kinetics of Mo dissolution into the Fe matrix during the milling process can be described by two regimes characterized by small values of Avrami parameter which do not exceed unit.