Control of the orientation of component molecules in Langmuir-Blodgett (LB) films is important for their use in molecular electronics. Cyclodextrins can be given a particular orientation at the air-water interface by introducing long alkyl chains through the amino, sulfinyl, and sulfide groups (see Figure). This article reviews progress in molecular-component and supramolecular LB films and photochemical switching systems constructed from them.