To explore the robust nature of template resorcinols in organic solid-state reactions, a series of mono- and dipyridines were cocrystallized with different substituted resorcinols. The organizational consequences of hydrogen-bonds in the hydroxyl···pyridine heterosynthon in the presence of competitive hydrogen-bonding functional groups are elucidated. C−O bond flexibility, steric hindrance, and formation of undesired intramolecular hydrogen bonds have strongly affected the ability of the template for a parallel alignment of olefins. Finally, structural changes that occurred at a molecular level during [2 + 2] photodimerization of the complex of 1,4-bis[(E)-2-(4-pyridyl)ethenyl]-2-fluorobenzene (bpef) with 2,4-dihydroxy-benzaldehyde were studied in detail by performing a rather rare single-crystal-to-single-crystal photoirradiation.