Supramolecular polymers are described that are derived from the association of two homoditopic heterocomplementary monomers through sextuple hydrogen-bonding arrays. They form fibers and a variety of different materials depending on the conditions. The strong affinity of the DAD-DAD (D=donor, A=acceptor) hydrogen-bonding sites for double-faced cyanuric acid type wedges drives the supramolecular polymeric assembly in apolar and chlorinated organic solvents. The marked influence of stoichiometry, as well as end-capping and cross-linking agents upon fiber formation is revealed in solution and by electron microscopy (EM). The results further contribute to the development of a supramolecular polymer chemistry that comprises reversible polymers formed through recognition-controlled noncovalent connections between the molecular components. Such materials are, by nature, dynamic and present adaptive character in view of their ability to respond to external stimuli.