In this research, crystallization of Fe36Cr12Mo10 and α-Fe phases in devitrification of Fe51Cr18Mo7B16C4Nb4 amorphous alloy was studied using X-ray diffraction and transmission electron microscopy. For evaluation of crystallization kinetics, differential scanning calorimetric tests were carried out at different heating rates. Results showed that two-step crystallization led to the formation of Fe36Cr12Mo10 and α-Fe phases in the structure of alloy. Activation energy of crystallization of Fe36Cr12Mo10 and α-Fe phases measured according to Kissinger-Starink model were 747 and 880 kJ/mol, respectively. Results growth mechanism along with the decreasing nucleation rate in crystallization of Fe36Cr12Mo10 and α-Fe phases.