This chapter reviews some recent experimental investigations of the orientational behaviors of thermotropic liquid crystals on surfaces that possess well-defined topography and chemical functionality. These orientational behaviors reflect competing long-range (elastic, electrostatic) and short-range, chemically specific (e.g., metal-ligand or hydrogen bond) interactions between the surface and liquid crystal. The defined nature of these surfaces makes possible the rationale manipulation of the orientational behavior of liquid crystals. We illustrate the opportunity in this area by using surfaces that present oriented carboxylic acid groups and metal carboxylates. Potential applications of these systems to gas-phase sensing of organophosphonate compounds are also described.