We synthesized two types of liquid crystalline nano-layers covalently bonded to Si and Si/SiO(2) wafers. Monolayers of terminal and lateral low molecular weight mesogens exhibit spontaneous homeotropic orientation, while planar orientation is obtained by means of rubbing process. On the other hand a novel polymer liquid crystal nano-layer, obtained via atom transfer radical polymerization (ATRP) of acrylate monomer from Si/SiO(2) surface, exhibits planar orientation of liquid crystalline side chain moieties. Structure of such novel composites was confirmed by optical studies as well as spectroscopic methods, including ellipsometry. The goal was to obtain low molecular weight liquid crystals alignment just from the mentioned above, modified surfaces.