Ferromagnetic properties and nanocrystallization process of soft ferromagnetic (Fe0.99Mo0.01)78Si9B13 ribbons are studied by transmission electron microscope (TEM), X-ray diffraction (XRD), Mössbauer spectroscopy (MS), differential scanning calorimeters (DSC) and magnetization measurements. The Curie and crystallization temperature are determined to be T C=665K and T x = 750K, respectively. The T x value is in well agreement with DSC measurement results. X-ray diffraction patterns had shown a good reconfirm of two metastable phases (Fe23B6, Fe3B) were formed under in-situ nanocrystallization process. Of which these metastable phases embedded in the amorphous matrix have a significant effect on magnetic ordering. The ultimate nanocrystalline phases of α-Fe (Mo, Si) and Fe2B at optimum annealing temperature had been observed respectively. It is notable that the magnetization of the amorphous phase decreases more rapidly with increasing temperature than those of nanocrystalline ferromagnetism, suggesting the presence of the distribution of exchange interaction in the amorphous phase or high metalloid contents.