The present work is a continuation of research on alloys based on iron, aiming at understanding the solidification behaviour of Fe-Cr-Nb alloys. Ternary Fe-Cr-Nb alloys with different concentrations were arcmelted and systematically characterized by means of; differential thermal analysis, optical and scanning electron microscopy coupled to an energy dispersive X-ray microprobe analysis and X-ray diffraction.For the first time, we suspect the presence of a metastable D'-phase in Fe-rich alloy. For higher vanadium and niobium contents a competition between two eutectics, E2 and E3, is clearly shown according to the observed microstructures and the solidification sequences.