Novel hybrid xerogel materials were synthesized by a sol-gel procedure. n-octadecyltriethoxysilane was co-condensed with and without different cross-linkers using Q(0) and T-0 mono-functionalized organosilanes in the presence of n-hexadecylamine with different hydroxyl silica functional groups at the surface. These polymer networks have shown new properties, for example, a high degree of cross-linking and hydrolysis. Two different synthesis steps were carried out: simple self-assembly followed by sol-gel transition and precipitation of homogenous sols. Due to the lack of solubility of these materials, the compositions of the new materials were determined by infrared spectroscopy, C-13 and Si-29 CP/MAS NMR spectroscopy and scanning electron microscopy.