Anion-responsive molecules comprising phenanthropyrrole rings were synthesized by oxidative coupling. Spectroscopic and theoretical examinations revealed the effects of the π-extended structures. In the solid state as ion-pairing assemblies, Cl- complexes of π-extended derivatives formed stacked structures composed of Cl- complexes themselves and those formed with countercations using extended π-moieties. Aliphatic anion-responsive molecules and their Cl- complexes, as ion pairs with the triazatriangulenium cation, provided hexagonal columnar structures with liquid-crystalline mesophases.