In the present work X-ray studies were performed on annealed Fe78Nb2B20 amorphous alloy prepared by melt-spinning technique. All the samples were annealed in vacuum for 1 hour at temperatures up to 800°C. For the studied alloy -Fe and Fe2B are the stable, crystalline phases. The -Fe crystallized as the first crystalline phase in the sample annealed at 350°C. On the other hand, metastable Fe3B phase appeared to be stable during annealing in 425-800°C temperature range. The best fitting of the experimental X-ray data to as jet available ICDD files was obtained for Ni3P type structure (39-1315 – S.G.: I (82)). New, experimental powder diffraction data for metastable Fe3B phase prepared according to ICDD standards were elaborated for the sample annealed at 600°C. For this sample the best agreement between the calculated values of lattice constants and positions of experimental diffraction lines was obtained. The X-ray data were collected using X-Pert Philips diffractometer equipped with curved graphite monochromator on diffracted beam. The Treor program was applied for the analysis of X-ray diffraction data.