Abstract.We have studied the electronic structure of Mo rich Mo 1−x Re x alloys (0≤ x ≤0.4) using valence band photoemission spectroscopy in the photon energy range 23-70 eV and density of states calculations. Comparison of the photoemission spectra with the density of states calculations suggests that with respect to the Fermi level E F , the d states lie mostly in the range 0 to -6 eV binding energy whereas s states lie in the range -4 to -10 eV binding energy. We have observed two resonances in the photoemission spectra of each sample, one at about 35 eV photon energy and other at about 45 eV photon energy. Our analysis suggest that the resonance at 35 eV photon energy is related to the Mo 4p-5s transition and the resonance at 45 eV photon energy is related to the contribution from both the Mo 4p-4d transition (threshold: 42 eV) and Re 5p-5d transition (threshold: 46 eV). In the CIS plot, the resonance at 35 eV incident photon energy for binding energy features in the range of E F (B.E. = 0) to -5 eV becomes progressively less prominent with the increasing Re concentration x and vanishes for x > 0.2. The difference plots obtained by subtracting the valence band photoemission spectrum of Mo from that of Mo 1−x Re x alloys, measured at 47 eV photon energy, reveal that the Re d like states appear near E F when Re is alloyed with Mo. These results indicate that interband s-d interaction, which is weak in Mo, increases with the increasing x and influences the nature of superconductivity in the alloys with higher x.