Technically useful hybrid micro- and nanocomposite materials might be prepared by solgel processing. Inorganic dopants (acids, metal salts) and organic modifiers (polyols, polyionens) as well as fillers (metal oxides, detonation diamond) were involved into the tetraethoxysilane (TEOS)- derived sols to modify sol-gel system properties. Influence of the above mentioned additives on parameters xerogels and films prepared (covering capacity, surface morphology, phase compositions, fractal parameters, and some others physicochemical properties) has been shown. Simultaneous use of dopants, organic modifiers and fillers has allowed preparing new hybrid nanocomposite materials. for microelectronics, electrical and power engineering.