The Cu clustering stage before the crystallization of Fe-Si-B-Nb-Cu amorphous alloys have been studied by three dimensional atom probe (3DAP) small-angle neutron scattering (SANS) and high sensitive differential calorimetry (DSC). Cu clustering occurs prior to the onset of the primary crystallization reaction. The number of the clusters estimated by 3DAP is large enough to provide heterogeneous nucleation sites to all bcc/D0(3) Fe-Si crystals which appear at higher temperatures. This fact indicates that the distribution of nanocrystalline Fe-Si is strongly affected by that of the Cu-enriched clusters. The average diameter and interparticle distance of the Cu-enriched clusters have also been estimated by SANS. An exothermic reaction is observed above the Curie Temperature in the DSC curves of the Fe-Si-B-Nb-Cu alloys. The onset temperature of the exothermic reaction is shifted to lower temperature with increasing Cu content. (C) 1999 Acta Metallurgica Inc.