Fe-Al-Si alloys have been recently developed in order to obtain excellent high-temperature mechanical properties and oxidation resistance. However, their production by conventional metallurgical processes is problematic. In this work, an innovative processing method, based on ultra-high energy mechanical alloying, has been tested for the preparation of these alloys. It has been found that the powders of low-silicon alloys (up to 10 wt. %) consist of FeAl phase supersaturated by Si after mechanical alloying. Fe2Al5 phase forms as a transient phase at the initial stage of mechanical alloying. The alloy containing 20 wt. % of Si and 20 wt. % of Al is composed mostly of iron silicides (Fe3Si and FeSi) and FeAl ordered phase. Thermal stability of the mechanically alloyed powders was studied in order to predict the sintering behavior during possible compaction via spark plasma sintering or other methods. The formation of Fe2Al5 phase and Fe3Si or Fe2Al3Si3 phases was detected after annealing depending on the alloy composition. It implies that the powders after mechanical alloying are in a metastable state; therefore, chemical reactions can be expected in the powders during sintering.