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Effect of electron irradiation on the crystallization and phase stability of Fe88Zr9B3 and Fe71Zr9B20 amorphous alloys was examined. Electron irradiation at an accelerated voltage of 2000 kV was performed at room temperature. The Fe71Zr9B20 alloy showed a wide supercooled liquid region and the ΔTx value was 71 K, while no glass transition was observed in Fe88Zr9B3 alloy. The amorphous phase in Fe–Zr–B alloys was not stable under irradiation and crystallization from the amorphous phase was accelerated by the irradiation. Nanocrystalline structure composed of α-Fe and cubic-Fe2Zr was formed in Fe88Zr9B3 alloy by irradiation induced crystallization, while no nanoscale precipitates of intermetallic compounds were formed during annealing. In Fe71Zr9B20 alloy, the formation of nanocrystalline precipitates was also confirmed by irradiation induced crystallization, although the formation of nanocrystalline structure had not been realized in high B concentration Fe–Zr–B alloys by annealing. These new results show that electron irradiation is effective in producing a new nanocrystalline structure.