Obtaining spontaneous orientation and fast collective response of ultra thin liquid crystalline (LC) layers to external stimuli without memory effects, is one of the major challenges in achieving the next generation of LC devices. The relationship between interfacial energies, structure and dynamics of support layers and their effects on surface orientation of liquid crystals has been investigated. A model polymeric system, containing a mesognic group, α- methylstilbene as anchoring group, bridged by an energy controlling moiety, fluorocyclobutyl, has been used to obtain substrates with controlled surface energy and structure. Neutron reflectivity was used to study the surface structure of the polymer. The orientation of a well characterized liquid crystal, 8CB that exhibits both nematic and Smectic phases, was studied by optical microscopy and small angle X-ray scattering. Correlation between the surface structure of the polymeric layer and the orientation of the Smectic phase indicated direct correlation between the surface orientation and the concentration of fluorine at the interface.