The valence band structures of the NiAl-Mo alloy was investigated by photoelectron spectroscopy. The valence band spectra of the NiAl-Mo alloy was shifted away from the Fermi level so that the Ni-d-band centroid moved to a higher energy by 0.22 eV as Mo was added. A possible explanation lied in the overlap of Ni-d bands in the energy with Mo-d and Al-p bands. The participation of Mo-d bands was correlated with the site preference of Mo in NiAl alloys.