In this work, the process of formation of metastable phases was investigated for the Fe75B25 composition. Mechanical synthesis was performed in a MAPF-2M high-energy planetary ball mill under an argon atmosphere. X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Mössbauer spectroscopy (MS) were applied to recognize the phases. After 6 h of milling, the material consisted of two phases, that is, metastable tetragonal t-Fe2B and amorphous phases. During further thermal processing, the metastable phase was transformed into the stable Fe2B phase.