Mössbauer spectrometry (57Fe and 119Sn) was used to investigate phase separation in coarse-grained Fe0.55Cr0.45 and in mechanically-alloyed nanocrystalline Fe0.55Cr0.45, Fe0.52Cr0.45Sn0.03 and Fe0.49Cr0.45Sn0.06 alloys during isothermal annealing at 748 K. Phase separation occurs faster in nanocrystalline Fe–Cr than in cold-rolled coarse-grained alloys. The effect of the interconnected microstructure on room-temperature hyperfine magnetic field distributions of alloys aged for hundreds of hours is qualitatively discussed. Tin hinders grain growth of nanocrystalline alloys.