Oriented salts from planar charged species were prepared by combining positively and negatively charged receptor-anion complexes with similar geometries using dicationic and electronically neutral π-conjugated receptors. Phenylene- or pyrimidine-bridged bis(imidazolium) dicationic anion receptors formed monocationic receptor-Cl(-) complexes that were accompanied by a free Cl(-). This free Cl(-) was subsequently captured by pyrrole-based neutral anion receptors to form negatively charged receptor-Cl(-) complexes. The ion pair of the resulting positively and negatively charged planar receptor-Cl(-) complexes could produce a supramolecular octane gel, adopting a lamellar self-organized structure in its xerogel state. On the other hand, the solid-state ion pairs had hexagonal columnar mesophases, which formed via alternate stacking of the positively and negatively charged planar receptor-Cl(-) complexes. By use of the flash-photolysis time-resolved microwave conductivity technique, the one-dimensional charge-carrier transporting property, with a mobility of 0.05 cm(2) V(-1) s(-1), was determined for the newly prepared solid-state ion pairs.