Grain boundary (GB) segregations were investigated by atom probe tomography in an Al–Mg alloy, a carbon steel and Armco® Fe processed by severe plastic deformation (SPD). In the non-deformed state, the GBs of the aluminum alloy are Mg depleted, but after SPD some local enrichment up to 20 at% was detected. In the Fe-based alloys, large carbon concentrations were also exhibited along GBs after SPD. These experimental observations are attributed to the specific structure of GBs often described as “non-equilibrum” in ultra fine grained materials processed by SPD. The GB segregation mechanisms are discussed and compared in the case of substitutional (Mg in fcc Al) and interstitial (C in bcc Fe) solute atoms.