The microstructure, phase composition, Mössbauer spectra, grain boundary segregation and magnetic properties of binary Fe–C alloys with carbon concentration of 0.05, 0.10, 0.20, 0.25, 0.45, 0.60, 1.3, 1.5 and 1.7 wt. % were studied in the as-cast state, after a long annealing at 725°C and after high-pressure torsion (HPT) at the ambient temperature and 5 GPa with 5 anvil rotations (shear strain about 6). The grain size after HPT was in the nanometer range. Only Fe3C (cementite) and -Fe remain in the alloys after HPT. It was also shown that the less stable Hägg carbide (Fe5C2) and retained austenite disappear, and phase composition closely approaches the equilibrium corresponding to the HPT temperature and pressure. Measurements of saturation magnetization and Mössbauer effect reveal that the amount of cementite decreases after HPT. The reason for partial cementite dissolution is the formation of the carbon-rich segregation layers in the ferrite grain boundaries.