The effect of the superstoichiometric Ti intercalation on the electronic structure of TiSe2 was studied by using X-ray photoelectron spectroscopy in nonresonant and resonant modes along with the DOS (density of states) calculations. It was shown that the presence of the Ti atoms in the interlayer space leads to the formation of the Ti 3d(z2)/Ti 3d(z2) hybridized band between the Ti atoms in the regular lattice positions and Ti atoms in the interlayer space. The charge transfer to the conduction band was not observed in this case.