Changes of the compositional and topological arrangement of the atoms during annealing of Fe-Si-B-(Me) amorphous alloys ribbons, changes of structure, magnetization and electrochemical parameters of dissolving were investigated. X-ray powder diffraction analysis of amorphous metallic alloy samples annealed at 873 K showed that the stability of the Fe3B-phase increases with increasing Ni content. The results obtained by the voltammetric method, not only correlate with the results of magnetic and X-ray diffraction studies, but also provide information on surface redox processes. (C) 2003 Elsevier B.V. All rights reserved.