Fe–Ga alloys, containing 18, 21, and 23 at.% of Ga, were prepared in bulk form. In their as-cast state, they display a small magnetostriction, that is strongly improved after annealing at 1000 [Formula: see text]C for 24 h, and subsequent rapid cooling. Multiple characterization techniques, such as x-ray diffraction, differential scanning calorimetry, Mössbauer spectroscopy, temperature-dependent magnetization curves, hysteresis loops, magnetic force microscopy, and magnetostriction measurements, were exploited in synergy to gain a deep understanding of the structure–property relationships in the studied alloys, before and after annealing. The A2 phase, which is favored in the lower range of compositions and is promoted at the expense of the [Formula: see text] one by annealing, is responsible for characteristic dendritic and maze magnetic domains, and for the strong improvement of the magnetostriction, which almost reaches 240 ppm (transverse configuration) in the alloys with 18 at.% of Ga, after annealing.