Bulk Fe-80at%Ni melts were undercooled by using cyclic superheating and glass slag purification technique, and the maximum undercooling 340 K could be achieved. The microstructures of Fe-80at%Ni alloys were observed by means of optical microscope (OM). The phase composition was identified by X-ray diffraction (XRD) analysis. The magnetic properties of Fe-80at%Ni alloys were measured by vibrating sample magnetometer (VSM) with a DC M-H analyzer. The results showed that there was only single γ-(Fe, Ni) phase existing in undercooled Fe-80at%Ni alloys. Two grain refinements and one grain coarsening were observed in the undercooling range from 28 K to 340 K. The first grain refinement could be ascribed to dendrite-remelting, and the second to recrystallization induced by the stress originating from rapid solidification. The grain coarsening could be considered as a result of solid-state grain coalescence. The measurement of soft magnetic properties showed that the grain size D decreases with an increase of undercooling, the maximum Ms is 109.98emu/g, corresponding to minimum grain size 42.9μm or undercooling 210 K, and the coercive force Hc is in proportion to the reciprocal of grain size D-1.