Surface Organometallic Chemistry (SOMC) methods have been applied, for the first time, in synthesis of liquid crystalline (LC) layers on silicon wafer surface. We have obtained unique materials with modified semiconductor (Si) surface, which can be applied in opto-electronics as switching and coupling devices as well as orienting optical elements in liquid crystalline cells. The covalently bonded LC monolayers can orient low molecular weight LC thin films up to -10 |im thickness. They are expected to be used primarily as a novel type of couplers and routers in laser telecommunication technology. The evaluation of the most effective analytical methods is also presented.