The enantiomer separation of a chiral Tröger's base analog and its use, as an optically active building block, in the construction of molecular superstructures are presented. Various strategies are illustrated here for the attachment of azo photoswitches to the Tröger's base scaffold without racemizing its stereogenic centers. The resulting optically active photoswitches introduced chirality, thermochromic, and phototunable properties to an achiral liquid crystal host. The doped mesophases reflected specific wavelengths of light owing to the formation of self-organized helical superstructures. These observations illustrate the potential use of the presented products as liquid crystal dopants.