The investigation of nanocrystalline materials is one of the very active areas in the material science and engineering. An important way of achieving nanocrystalline structure is to properly anneal a corresponding amorphous material. In this paper, a detailed thermal analytical study to the crystallization annealing of so far widely interested Fe-Zr-B material was reported, in order to supply valuable information of obtaining optimum microstructure and to be instructive to annealing processes.