The nanocrystallization process of the amorphous Fe -Mo-Si -B alloy under ball milling is characterized by means of transmission Mössbauer emission spectroscopy (TMES) in the present paper. It was found that a single a-Fe phase with the bcc structure is formed under ball-milling the amorphous Fe-Mo -Si-B alloy. A significant increase in the relative area of the subspectra of 8Fenn and 7Fenn and a remarkable decrease in isomer shift and half linewidth of the subspectra of various Fe configurations, especially in the case of 6Fenn, were observed during the ball-milling process. The diffusion of metalloid atoms from the bcc a-Fe phase to the remaining amorphous phase and a-Fe͞a-Fe grain boundaries is suggested to occur during the mechanical crystallization of the current amorphous alloy based on the above TMES investigations.