High resolution imaging and electron diffraction confirm that in the as-quenched state the structure of Fe79.7−xCrxNb0.3B20 (x = 11–13 at. %) melt-spun ribbons is completely amorphous, independent of the Cr content. Energy-dispersive X-ray spectroscopy mapping emphasizes clearly the presence of Fe and Cr clusters varying from approximately 1 to 2–3 nm in size with the increase of Cr content from 11 to 13 at. %. The Fe and Cr atoms segregate the atomic scale to form nanometer sized clusters, influencing strongly the macroscopic magnetic behavior. The Curie temperature of the system, TCsystem, confirmed by the magnetic susceptibility versus temperature measurements, gives the strength of the magnetic interactions between clusters. The inter-cluster interactions are much stronger for lower contents of Cr, the microstructure is less uniform, and TCsystem increases from 290 K for 13 at. % Cr to 330 K for 11.5 at. % Cr. The whole system transforms to a ferromagnetic state through interactions between the clusters. Zero-field cooling and field cooling curves confirm the cluster behavior with a blocking temperature, Tb, of about 250 K. Above Tb, the ribbons behave as a superferromagnetic system, whilst below the blocking temperature a classical ferromagnetic behavior is observed.