The electronic structure of titanium nitride layers formed on the TiNi substrates is examined by Auger electron spectroscopy and electron emission distribution methods. Spectral analysis shows that the on-top carbon layer has a graphite structure and the neighbouring layer is constituted of titanium nitride. The shape of the main valence spectra was explained by the Hubbard model. From the comparison of experiment and theory the model parameters were estimated. Besides, the existence of surface and internal plasmons verifies the layered structures with average dielectric constants.