A 2,6-naphthalenediol-modified BisPYBOX (2,6-bis(benzoxazol-2-yl)pyridine (benzoPYBOX)) ligand and a naphthaldiimide-modified BisPYBOX ligand were newly designed and synthesized as a bar for ladder structure formation. The mixing of these two BisPYBOX ligands formed supramolecular ladders along a polymeric secondary dialkylammonium cations as templates to yield charge-transfer (CT) complexes in solution.