Ni-30wt%Fe elemental power mixture was mechanically milled under argon atmosphere for variuos times up to 25h.The evolution of Ni-Fe alloying during milling and the microstructure of the as-milled powders were characterized by XRD, EPMA (electron probe microanalysis), SEM and TEM, respectively. The results show that nanocrystalline Ni (Fe) supersaturated solid solution alloy powders with 30wt. % Fe in composition can be synthesized by mechanical milling of the elemental powder mixture. Both the content of Fe dissolved and the microstrain developed in the as-synthesized Ni (Fe) solid solution phase increase, while the crystallite size decreases, steadily with increasing milling time. In particular, the Ni-30wt%Fe alloy powders obtained by 25h milling consist of a single Ni (Fe) supersaturated solid solution phase with average crystallite size of about 15nm and accumulated microstrain as high as 1.12%. DSC tests show that the nanocrystalline Ni-30wt%Fe alloy powders have a lower melting temperature than the elemental powder mixture, attributed to the unique Ni (Fe) solid solution phase structure, the nanocrystallization, and the high strain energy.