In this study, the exothermic DSC peaks observed in rapidly-solidified Fe-44.9at.%Al ribbons and water-quenched Fe-48.5at.%Al single crystals were analyzed by Matusita’s method in order to discuss the kinetics of the agglomeration processes of supersaturated vacancies. Both the nucleation and morphological factors, n and m, respectively were approximately 3 for the rapidly solidified ribbons and were approximately 2 for the water-quenched single crystals. Based on the Matusita’s idea, the m values suggest the growth of 3-dimensional voids in the rapidly solidified ribbons and the growth of 2-dimensional dislocations loops in the single crystals due to the agglomeration of supersaturated vacancies. In addition, the n values suggest that the nuclei of voids and dislocation loops existed in as-quenched samples. These interpretations are in good agreement with the results of TEM observations.