Herein, we adopted alloying and rapid-dendrite-growth methods to improve the mechanical properties of Febased alloys. Three molten alloys including Fe-5Ni-5Mo-5Ge, Fe-5Ni-5Mo-5Ge-5Co, and Fe-5Ni-5Mo-5Ge-5Co-5Si were undercooled, during which (αFe) dendrites grew rapidly with the decrease of temperature (i.e., increase of undercooling). The rapid growth of (αFe) dendrites in the Fe-5Ni-5Mo-5Ge-5Co alloy at a high rate of 31.8 ms −1 caused by a large undercooling more effectively enhanced the microhardness than a Co addition did. In comparison, because of the great disparity of atom size and valence electron number between Fe and Si, a further Si addition suppressed the (αFe) dendrite growth while dramatically increasing the Vickers microhardness of the Fe-5Ni-5Mo-5Ge-5Co-5Si alloy to H V 622.