The supramolecular chemistry of acyclic oligopyrrole derivatives mainly reported by the author’s group in the last four years has been summarized in this review. The author has demonstrated the “first step” to construct the new materials and concepts based on the new molecular systems consisting of pyrrole rings, which form the complexes, assemblies, and organized structures, by using noncovalent interactions such as metal coordination, hydrogen bonding, and π–π interaction. Acyclic π-conjugated oligopyrroles have exhibited not only host–guest binding behaviors in solutions but also the formation of, for example, (i) metal coordination polymers to give emissive colloidal spheres, (ii) solid-state assemblies of acyclic π-conjugated anion receptors and their anion complexes, (iii) anion-responsive supramolecular gels from the receptors with aliphatic chains, and (iv) solvent-assisted organized structures like vesicles derived from amphiphilic anion receptors.