In summary, we prepared two partially fluorinated dehydrobenz [18]annules 1 and 2 via a one-pot route. Their single crystal structures show that the two macrocycles organize into columnar stacks, which are critically enabled by the presence of the fluorinated rings. In macrocycle 1, those rings engage in apparent [π•••π] stacking fluoroarene-alkyne interactions. While the fluoroarene-arene interaction was found to direct the columnar stacks in the most symmetric hexameric macrocycles, in the case of diamond-shaped macrocycles with orthoand meta-linked fluoroarene and arene groups, the columnar stacking has been achieved via fluoroarene-alkyne interaction. Our ongoing work aims to explore the generality of this assembly pattern and its relevance in the construction of advanced materials.