A novel cationic homopolymeric system has been constructed from a simple linear cationic pyridylphyridinium system by forming hydrogen bonds between the carboxylic acid termini of one molecule and the pyridine nitrogen atom of an adjacent molecule. The synthesis and characterization of the initial linear system are described and the X-ray crystal structure of the final tape system presented. This work illustrates how molecular recognition can be utilized to assemble supramolecular structures with a degree of predictability.