High-pressure torsion has been used to obtain the ultra-fine grained (UFG) state with a high specific area of grain boundaries (GBs) in Al-Zn, Al-Mg, Cu-Ag, Cu-Co, and Cu-Ni solid solutions with face-centered cubic (fcc) lattices. The UFG samples were heated in a differential scanning calorimeter (DSC). Small endothermic peaks in the DSC curves were observed in the one-phase solid-solution area of the respective phase diagrams, i.e., far away from the bulk solidus and solvus lines. A possible explanation of these endothermic peaks is based on the hypothesis of phase transformations between GB complexions. This hypothesis has been supported by observations with transmission electron microscopy and electron backscattering diffraction. The new lines of GB phase transformations have been constructed in the Al-Zn, Al-Mg, Cu-Ag, Cu-Co, and Cu-Ni bulk phase diagrams.