In conjunction with Auger electron spectroscopy measurements, we have developed a procedure for obtaining a clean Nb surface using an electron bombardment heating technique. We have then studied the valence band photoemission as a function of photon energy. We find that calculations for the bulk theoretical density of states are in basic agreement with the ultraviolet photoemission spectroscopy data. We have also studied the initial oxidation of the clean Nb surface. Structure in the energy distribution curves suggests three stages in the oxidation process. Furthermore, the valence band energy distribution curves for clean Nb3Sn prepared ’’insitu’’ were measured and showed a strong resemblance to pure Nb as has been observed previously in x‐ray photoemission. Evidence is found for the existence of Nb2O5and SnO2in the surface oxides of Nb3Sn.