The effect of Cu and Nb alloying additions on the crystallization of Fe-Si-B based alloys were studied. DSC, XRD, TEM, EELS and VSM techniques were used to study the thermal properties, phase formation during primary crystallization, morphological transitions and magnetic properties. The additions of individual Cu or Nb alloying additions changed the crystallization temperature as well as the activation energy for primary crystallization. The phases formed during primary crystallization for the Fe77.5Si13.5B9, Fe76.5Si13.5B9Cu1 and Fe74.5Si13.5B9Nb3Cu1 alloys are the same, however the morphologies are significantly different. Alloying additions of 3 at.% Nb induced a change in the crystallization mechanism and the type of phases formed. The combined additions of Cu and Nb resulted in the formation of nanocrystals. B atoms were found to be rejected around dendrites formed during primary crystallization of the Fe77.5Si13.5B9 alloy. The highest saturation magnetization and the lowest coercivity is obtained in the Fe(77.5)Sil(3.5)B(9) and Fe74.5Si13.5B9Nb3Cu1 alloy respectively after annealing at 550 degrees C for 1 h. (c) 2005 Elsevier B.V. All rights reserved.