Ion-based materials were fabricated through ion pairing of planar receptor-anion complexes and cation modules as negatively and positively charged building blocks, respectively. Anion receptors that could not form soft materials by themselves provided mesophases upon anion binding and subsequent ion pairing with aliphatic cation modules. The mesogenic behaviors were affected by structural modification of both the cation module and the anion receptor. Synchrotron X-ray diffraction measurements suggested the formation of columnar mesophases with contributions from charge-by-charge and charge-segregated arrangements. Flash-photolysis time-resolved microwave conductivity measurements further revealed a higher charge-carrier mobility in the assembly with a large contribution from the charge-segregated arrangement than in the charge-by-charge-based assembly.