In this work, we reported the results obtained by the structural characterization of the FeAl3 intermetallic compound. This material was synthesized by conventional casting technique using Fe (99.97%) and Al (99.92%) elemental metals. Then, the as-cast alloy was subjected to high-energy ball-milling for different times (1, 2.5, 5, 7.5, 10 and 15 h). The characterization of the alloy was performed by X-ray diffraction patterns, scanning and transmission electron microscopy. The results show that FeAl3 intermetallic was produced as a single-phase after conventional casting. The milled experiments show that the FeAl3 (monoclinic) transforms to Fe2Al5 (orthorhombic) after 15h of milling. Therefore, this phase transformation is characterized by a change from low to high symmetry systems.