Mechanical alloying of a number of blended elemental powders of Fe-based alloy systems containing four or five components was undertaken to determine if amorphous phases could be produced and also to compare the glass-forming ability achieved by mechanical alloying and that obtained by solidification-processing methods. Amorphous phase formation was achieved in all the alloy systems investigated, the time for the amorphous phase formation being a function of the glass-forming ability of the alloy system investigated. However, in some alloy systems it was noted that on milling, beyond the time required for the formation of the amorphous phase, the amorphous phase started to crystallize, a phenomenon designated as mechanical crystallization. The present paper specifically discusses the results of mechanical crystallization obtained in the Fe42Ge28Zr10B20 and Fe42Ni28Zr10C10B10 alloy systems as representatives of the typical quaternary and quinary (five-component) systems, respectively. In the case of the quaternary system, mechanical crystallization led to the formation of a supersaturated solid solution of all the solute elements in Fe, while in the quinary system, a mixture of the solid solution and intermetallic phases has formed. The possible reasons for mechanical crystallization and the reasons for the differences in the behavior of the quaternary and quinary systems are discussed.