We report on the synthesis and properties of formyl‐substituted dipyrrolyl diketone–BF2 complexes (anion receptors) and their extended derivatives. The formyl‐substituted receptors exhibited efficient anion‐binding behavior and complicated solid‐state hydrogen‐bonding assembly patterns, due to the formyl group's electron‐withdrawing and hydrogen‐bond‐accepting properties. The extended derivatives, prepared by the formation of Schiff bases and their subsequent reduction, behaved as building subunits to provide gel‐like materials in spite of the existence of β‐ethyl substituents. Fairly unspecific spherical particle morphologies were observed for these gel‐like materials by optical microscopy and AFM. The anion‐responsive behavior of the supramolecular assemblies (gelated materials) was also examined.