An X-ray photoelectron spectroscopy (XPS) method was used to investigate the electronic structure of niobium diselenide 4H(b)-NbSe₂ synthesized at high pressures (7,7 - 9,0 GPa). For comparison, the electronic structure of an initial polymorphous form of niobium diselenide, 2H-NbSe₂, was also studied. The XPS core-level binding energies (BEs) and valence-band structures for the two NbSe₂ modifications have been determined. The XPS core-level BEs of pure niobium and selenium were also investigated. It is shown that, in the 2H-NbSe₂ and 4H(b)-NbSe₂ diselenides, a charge transfer occurs from Nb to Se atoms. The XPS core-level BEs of both niobium and selenium atoms remain constant (within the experimental errors) for the above NbSe₂ polytypes studied. In the sequence 2H - NbSe₂ -> 4 H(b) - NbSe₂ a small increase of the XPS valence-band half-width was observed. The present experimental results are compared with earlier theoretical studies of niobium diselenide.

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