Control of number and order in the supramolecular assemblies have been of much interest due to their application for informational technology and mimetic approaches for molecular information of biological polymers such as DNA and proteins. We previously reported that 2,6-bis(2-oxazolyl)pyridine (Pybox) forms the 1:1 complexes with various secondary dialkylammonium cations as a tool for supramolecular assemblies. In this report, we demonstrate formation of ordered supramolecular assembly from two different pybox (P) and bzpybox (B) ligands by complexation with dimeric imminium cation (IA) as a template. The two ammonium sites of IA were differentiated by steric repulsion between the phthalimide moieties of IA and macrocyclic structure of P. 1H-NMR titration indicated that IA form a 1:1:1 complex with P and B.