Complex compounds of Te (IV) with organic nitrogen-containing cations are of great interest due to the presence of intensive luminescence in them which enables to use them in contemporary energy efficient fluorescent lighting, plasma display panels, cathode-ray tubes, X-ray screens. But the questions relating to mechanism of luminescence, influence of crystal field of ligands on probability of optical transitions in a system, role of ligand-metal charge transfer state, emergence of Jahn-Teller effect and spin-orbital interaction remain unexplored up to the present. Computation of the electron structure of complexes was performed with the help of Density Functional Theory Method (DFT) using bundled software FireFly 7.1G, TZVP basis by F. Weigend and R. Ahlrichs with addition of polarized functions for all atoms and Effective Core Potential (ECP) for tellurium atom was used as a basis set. B3LYP5 hybrid exchange-correlated functional of the third generation was used as a functional.figureFig.1. X-ray photoelectron spectra of valence band of the complexes: a) TeBr6(CN3H6)2 b) TeBr6Cs2 X-ray photoelectron spectra of the complexes were received using high-vacuum twocompartment MXPS XP system of research (Omicron, Germany). Radiant energy - 1253,6 eV (MgKa). Chamber pressure when conducting the experiment did not exceed 4х10–9 mb. Overview spectra and parts of spectra were recorded with analyzer transmission energy of 50 eV and 20 eV respectively. Spectrometer instrument function in the write mode of atom characteristic level lines, defined at the contour of the line Ag3d5/2, had the width of 1,2 eV at the half-height. С1s level of carbon was chosen for calibration of electron binding energy scale. Interpretation of X-ray photoelectron spectral bands of the complexes under research was performed and the character of respective spectral bands was explored on the basis of conducted quantum-chemical calculations of model complexes.