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The composition of the surface and electrical properties of silicon oxide nanocomposites of porous silicon were investigated by FTIR spectroscopy in the range of 400 – 4000 cm-1and by impedance spectroscopy in the frequency range of 25 Hz – 1 MHz. It was revealed the different dispersion of electrical capacitance in different frequency bands and the complex relaxation processes that affect the electrical transport properties of nanocomposites. The correlations between the IR absorption spectra of silicon oxide composites and processes of charge transfer was defined. On the basis of analysis of spectra of thermal stimulated depolarization it was shown that oxidation of the surface of porous silicon nanocrystals gives rise to changing the density of states in different energy ranges.