Fe–Cr–Mo–B–C amorphous powders are usually used in thermal spraying, spark plasma sintering or 3D printing to prepare coatings or large-sized bulk amorphous alloys. However, their non-isothermal crystallization kinetics is far from being investigated in detail because of their relatively complicated crystallization behavior. In this work, the phase evolution, crystallization kinetics and crystallization mechanism of Fe–Cr–Mo–B–C (Cr: 25–27 wt%, Mo: 16–18 wt%, B: 2–2.2 wt%, C: 2–2.5 wt%) amorphous powder during non-isothermal crystallization are analyzed by X-ray diffraction, scanning electron microscope and differential scanning calorimetry together with Ozawa method and local Avrami exponent. The peak temperature of the first precipitated phase is less sensitive to the heating rate. In the non-isothermal crystallization process upon constant-rate heating to elevated temperatures the phase sequence is: α-Fe, M23(C, B)6, M7C3 and FeMo2B2 (M = Fe, Cr, Mo). The apparent activation energy of crystallization of the amorphous powders obtained using Kissinger’s method is between 385 and 557 kJ/mol, which is higher than that of most iron-based amorphous alloys reported so far, indicating a relatively high stability against crystallization. a-Fe and FeMo2B2 have a similar transformation mechanism: the early phase transition is completed by diffusion controlled growth with an increasing nucleation rate; as the crystallized volume fraction increases, the nucleation rate decreases, and nucleation does not occur even in the later stage of crystallization. The crystallization mechanism of M23(C, B)6 and M7C3 is similar: when the crystallized volume fraction α is higher than 0.1, only crystal growth occurs. This might be due to the fact that the large number of interfaces formed between the early precipitated phase and the amorphous matrix promote nucleation, rendering nucleation complete at the stage when the crystallized volume fraction α is less than 0.1. Therefore, the first and fourth crystallization events are diffusion controlled, the second and third crystallization events are primarily governed by grain growth.