We report a detailed synthesis and characterization of novel polymeric supramolecular structures composed of semiconducting perylene diimide (PDI)-imidazole templates of varying methylene spacer length (n = 3, 4, and 6) hydrogenbonded to a conjugated polymer backbone of acid-functionalized polydiacetylene (PDA), 10,12 pentacosadiynoic acid. First, a combination of molecular and morphological characterization tools confirmed that the templated supramolecular structures are a result of the synergistic effect of intermolecular PDI pi-pi stacking coupled with noncovalent imidazole-acid interactions. Second, a simple and scalable solid-state polymerization of the drop-cast films by UV radiation delivers multichromic, multiresponsive films capable of unique phase/morphology-switching properties with a high degree of local ordering. Thermal studies by differential scanning calorimetry and morphological studies by wide- and small-angle X-ray scattering (WAXS/SAXS, respectively) show dramatic morphological effects and trends in crystallinity with methylene spacer group extension. Furthermore, UV-vis studies displayed an unusual PDA "purple phase" transition, which was additionally verified by SAXS as a coexistence of previously known red- and blue-phase PDA. Finally, the polymerized drop-cast films displayed reversible thermo- and solvatochromic responses after a second treatment of UV radiation and additional UV-thermal cycling revealed the extent of reversibility.