Herein we present a new, readily functionalized AAA–DDD hydrogen bond array. A novel AAA monomeric unit (3a–b) was obtained from a two-step synthetic procedure starting with 2-aminonicotinaldehyde via microwave radiation (overall yield of 52–66%). ¹H NMR and fluorescence spectroscopy confirmed the complexation event with a calculated association constant of 1.57 × 10⁷ M⁻¹. Likewise, the usefulness of this triple hydrogen bond motif in supramolecular polymerization was demonstrated through viscosity measurements in a crosslinked supramolecular alternating copolymer.