Al-27-MAS (magic angle spinning)-NMR and Fe3+ EPR measurements have been performed to follow the local process of corundum formation starting from xerogel on the Al3+ and Fe3+ sites yielding complementary information. Different heat treatments have been applied to the samples: an isochronous procedure and thermoanalytical measurements stopped by quenching. Despite the different mechanisms of the phase transitions deduced, both seeding and Fe3+ doping under the conditions of isochronous procedure favor the formation of alpha-Al2O3 at remarkably low temperatures. The. first observed temperature of corundum formation following the isochronous procedure with iron-doped samples is as low as 750 degrees C. The transition alumina, which could be clearly evidenced, is the gamma-Al2O3 phase (four-and six-fold Al coordination). In undoped or unseeded samples, intermediate Fe species could be detected by ESR and evidence for theta-Al2O3 was obtained from Al-27-NMR spectroscopy.