The aim of the present paper is to find correlations between structural changes and electrical, mechanical and magnetic properties in Fe78Si13B9, Fe76Nb2Si13B9, Fe75Cu1Nb2Si13B9, Fe75Cu1Zr1Co1Si13B9, amorphous and nanocrystalline alloys obtained by melt spinning technique. The influence of annealing on material brittleness, magnetic and electric properties was examined. It was found that the optimization of soft magnetic properties effect is a thermally activated process and its diffusion parameters were determined. It was shown that for the alloys containing Cu, Nb and Zr as alloying additions, the optimization process can be attributed to formation of a nanocrystalline phase. In contrast to this for the FeSiB and FeNbSiB alloys the optimization process should be related to the relaxed amorphous phase.