The paper reports on a study of the electronic structure of binary homogeneous alloys Ti 55 Ni 45 , Ti 50 Ni 50 , and Ti 45 Ni 55 by X-ray photoelectron and near-edge X-ray absorption spectroscopies. The experimental data obtained were used to derive the occupied and unoccupied d-states density redistribution upon formation of the Ti–Ni alloys. The Ti and Ni L 2,3 X-ray absorption edge intensity measured permitted calculation of the variation of the titanium and nickel d-shell occupancy induced by formation of the Ti 50 Ni 50 , Ti 55 Ni 45 and Ti 45 Ni 55 alloys. It is shown that the occupation of the nickel d-band decreases by 0.13el./atom in formation of the above alloys and practically does not depend on the ratio of the constituent elements, whereas that of the titanium d-shell is strongly dependent on the atomic composition of the alloy. The charge transfer between the components was found to be insignificant; this implies that the change in occupancy of the nickel and titanium d-shells originates from intratomic redistribution of electron density between the d- and sp-states. The Ti 50 Ni 50 equiatomic alloy is unique in that it has the lowest titanium d-shell occupancy and, hence, the largest number of sp-electrons. It is shown that the increasing Ni content in the TiNi alloys leads to a noticeable gain of titanium d-electrons. It is assumed that the additional d-electrons can form a direct bonds, which increases the elastic moduli and, consequently, reduce the temperature of martensitic transformation in Ni-rich TiNi alloys.