α-Fe surfaces were implanted at room temperature (RT) and at 300 °C with 50 keV Al+ ions with a nominal dose of 5×1017 cm-2. The samples were studied in the as-implanted state and after annealing at 300 °C. The depth distribution of the Fe–Al phases formed was investigated nondestructively at RT and at 40 K by depth-selective 57Fe-conversion–electron Mössbauer spectroscopy (DCEMS) in the energy range of K- as well as L-conversion electrons. Integral conversion–electron Mössbauer spectroscopy (CEMS) was performed between 30 K and RT. In addition, secondary neutral mass spectroscopy and depth-profiling Auger-electron spectroscopy were employed for investigating the element–concentration depth profiles which were observed to extend deeper than Monte Carlo simulations predict. We found an atomically disordered magnetic and an atomically disordered nonmagnetic bcc phase in the as-implanted state the composition of which can be explained by the Al-concentration dependence of bulk disordered Fe–Al alloys. After annealing the nonmagnetic phase becomes atomically ordered (B2 structure) whereas the magnetic phase stays in the atomically disordered state. The layer-like structure of the two phases observed after annealing can be described by the magnetic phase diagram of ordered Fe–Al alloys. © 1998 American Institute of Physics.