Abstract： In this paper, the M?ssbauer spectra of amorphous Fe81-xNixSi3.5B13.5C2 (x = 5, 10, 15, 20, 25, 30, 35) alloys and crystalline Fe50Ni50 are studied at room temperature and under external magnetic field. The hyperfine interaction parameters and hyperfine field distribution curves were obtained with the fitting spectrum method. The results indicated that there are two magnetic states of iron atom and Inver-like characteristic in amorphous Fe-Ni-Met alloys. Anomalous phenomena at about 15 at % Ni in Fe-Ni-Met alloys was revealed. It was suggested chat the conditions of external magnetic field and low temperature have the similar effect on the ordering of magnet. In the sometime, the mechanism of hybridization of the Fe 3d hand with the metalloid valence orbitals and the electron tranfer between transition metals was used to explain the experimental results for the amorphous transition metals (TM)-metalloid (Met) alloys.