The crystal structure and the magnetic properties of the low‐temperature α‐FeB phase obtained by working in a mill are investigated by X‐ray diffraction analysis, Mössbauer study, and magnetic measurements. The crystal structure of α‐FeB is determined as a CrB(Bf) structure type with a = 0.2951 nm, b = 0.7564 nm, and c = 0.2953 nm. Parameters of the hyperfine interactions in α‐FeB are also determined. The Mössbauer data analysis suggests that the observed change of Heff in α‐FeB in comparison with the value for the β‐modification is related with the change of orientation of the magnetic moments of Fe atoms making an angle of ≈40° with respect to the crystallographic b‐axis. It is shown that β‐ and α‐FeB have close values of magnetization and Curie temperature Tc = 580 K.