Fe-based Fe85B15, Fe84B15Cu1, Fe82Si2B15Cu1, Fe85Si2B12Cu1, and Fe85Si2B8P4Cu1 (NANOMET®) alloys were experimental and computational analyzed to clarify the features of NANOMET that exhibits high saturation magnetic flux density (Bs) nearly 1.9T and low core loss than conventional nanocrystalline soft magnetic alloys. The X-ray diffraction analysis for ribbon specimens produced experimentally by melt spinning from melts revealed that the samples were almost formed into an amorphous single phase. Then, the as-quenched samples were analyzed with differential scanning calorimeter (DSC) experimentally for exothermic enthalpies of the primary and secondary crystallizations (ΔHx1 and ΔHx2) and their crystallization temperatures (Tx1 and Tx2), respectively. The ratio ΔHx1/ΔHx2 measured by DSC experimentally tended to be extremely high for the Fe85Si2B8P4Cu1 alloy, and this tendency was reproduced by the analysis with commercial software, Thermo-Calc, with database for Fe-based alloys, TCFE7 for Gibbs free energy (G) assessments. The calculations exhibit that a volume fraction (Vf) of α-Fe tends to increase from 0.56 for the Fe85B15 to 0.75 for the Fe85Si2B8P4Cu1 alloy. The computational analysis of the alloys for G of α-Fe and amorphous phases (Gα-Fe and Gamor) shows that a relationship Gα-Fe∼Gamor holds for the Fe85Si2B12Cu1, whereas Gα-Fe<Gamor for the Fe85Si2B8P4Cu1 alloy at Tx1 and that an extremely high Vf=0.75 was achieved for the Fe85Si2B8P4Cu1 alloy by including 2.8 Si and 4.5 P into α-Fe. These computational results indicate that the Fe85Si2B8P4Cu1 alloy barely forms amorphous phase, which, in turn, leads to high Vf and resultant high Bs.