Novel SiO₂/silane/POSS functional hybrids have been synthesized via an immobilization method. Hybrid materials were obtained through a connection of emulsion silica with defined dispersive and morphological properties with (3-isocyanatepropyl)triethoxysilane and selected mono- or octasubstituted POSS compounds in organic solvent. Modification effectiveness of the obtained SiO₂/silane/POSS hybrid systems was confirmed with the use of the Fourier transform infrared spectroscopy (FTIR). In order to determine the influence of bifunctionalization on coverage degree of the selected POSS compounds, elemental analysis (C, H, N contents) was performed. Moreover, parameters of porous structure of the obtained products were determined: BET surface area, total volume and mean size of pores. During analysis the thermal stability of silsesquioxanes cage, unmodified silica support, and hybrid systems have been investigated. For this purpose dispersive and morphological characterization (particle size distribution and TEM images) was performed.