The electron structures of amorphous Nb100-xNix (x= 65, 59.8, 56.4) alloys are studied by means of UV-Photoelectron spectroscopy (UPS). It is found that the position of the Fermi level is located near the minimum of the density of states, which explains the double Curie-point phenomena in Nb-Ni alloys. Analysing the electron structure of Nb-Ni alloys, it is pointed out that the hybridization of two d-bands with energies close to each other may form a new hybridizated band near EF and the hybridization is related to the valence difference. The charge transfer makes the peaks of bands shifting. The density of states of TE-TL. alloys at EF should include two parts of contributions, i.e., that from 3d electron stsates, which is of advantage to magnetism, and that from 4d electron states, being of advantage to superconductivity. Different ratio of these contributions at Er influences the magnetism and superconductivity of the alloys greatly. The coexistence of localized magnetic moments and superconductivity has also been discussed.