The electronic energy structure of Ti-Ni and TiNi-Cu alloys has been studied experimentally by XPS and NEXAFS and theoretically by the full-potential local-orbital minimum-basis code. The study has revealed formation in the valence band of the Ti50Ni50 alloy of a common d-band through hybridization of the d-states of Ti with those of Ni, which is localized within a narrow binding-energy interval. This brings about an intra-atomic redistribution of Ti electron density in the Ti50Ni50 alloy compared to the pure metal: decrease of the occupancy of the Ti d-shell is countered by an increase in the number of Ti p-electrons. The occupancy of the Ti d-shell in the TiNi-Cu alloys, where Ni atoms are partially substituted by Cu, and in the Ti-Ni alloys with an excess of the Ni is more than in the equiatomic Ti50Ni50 alloy. The occupancy of the Ni and Cu d-shells in the Ti-Ni and TiNi-Cu alloys is independent of the atomic composition. The Ti d-shell sensitivity to variation of the nearest atomic environment is apparen