For the purpose of elucidating the mechanisms for molecular organization at poled ferroelectric surfaces, single crystalline lithium niobate (LN), 'Z-cut' along the (0 0 0 1) plane, has been prepared and characterized and subsequently exposed to liquid crystal molecules. As a model system we chose to study the anchoring of 4-n-octyl-4 0 -cyanobiphenyl (8CB) to LN. Liquid crystalline films are of interest because of their useful electronic and optical properties as well as chemical sensing attributes. Low-energy electron diffraction (LEED), atomic force microscopy (AFM), surface contact angle measurements (CA), and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface of lithium niobate as well as the nature of 8CB films grown on the surface. Atomically flat LN surfaces were prepared as a support for monolayer thick, 8CB molecular domains. 8CB liquid crystal molecules were deposited by an ambient vaporization technique and the films were analyzed using XPS and CA. Understanding electrostatic anchoring mechanisms and thin film organization for this molecule on uniformly poled surfaces allows for a fuller appreciation of how molecular deposition of other polarizable molecules on periodically poled and patterned poled lithium niobate surfaces would occur.