The synthesis of nanocrystalline Fe, Fe–4 wt% Al, and Fe–10 wt% Al solid solutions by SPEX ball milling has been studied. The microstructural evolution during ball milling, as well as subsequent heat treatment, has been characterized. The results demonstrate that ball milling promotes the formation of αFe–4 wt% Al and αFe–10 wt% Al solid solutions by reducing the activation energy of these alloys and generating thermal energy during this process. For Fe–10 wt% Al powders milled for various time intervals up to approximately 20 min, the FeAl intermetallic compound is formed. For alloys annealed at temperatures ranging from 600 to 1000 °C, the addition of 10 wt% Al to Fe significantly enhances the thermal stability of the nanocrystalline Fe–Al alloys. Interestingly, the addition of Al within the range of 4–10 wt% seems to have little effect on the thermal stability of these alloys annealed under the same conditions. Also, the thermal stability improves for alloys milled in air as opposed to those processed using Ar.