Bulk Fe-50at%Ni alloy melts were undercooled using cyclic superheating and glass slag purification. As a result, a maximum undercooling up to 217 K could be achieved. As-solidified microstructures were observed by means of optical microscope. Phase identification of Fe-50at%Ni alloys was performed using the Shimadzu X-ray diffractometer (XRD) system. The chemical constitution revealed using a JEOL Model JSM-6700F scanning electron microscope equipped with energy dispersive X-ray spectroscopy (EDX). The magnetic properties of the alloys were measured by vibrating sample magnetometer (VSM) with a DC M-H analyzer. The results indicated that there were twice grain refinements occurred within an undercooling range of 55-217K, where the first could be ascribed to dendrite-remelting, and the second to recrystallization. The phase composition of undercooled Fe-50at%Ni alloys comprised two phases, i.e., solid solution phases with bcc and fcc structure. At various undercoolings, the saturation magnetization Ms and Hc related closely to the measured grain size D, and they were in proportion to D-1 by the regression analysis.