Two different halides containing chloride-and bromide-assisted dissimilar crystalline supramolecular building blocks of 4′-(1H-imidazol-2-yl)-4,2′:6′,4″-terpyridine (ITP) have been achieved. The dissimilar supramolecular associations with hydrogen-bonded networks have been engineered by the role of halides in the ITP-based crystal systems (i.e., ITP-Cl and ITP-Br for Cl − and Br − , respectively). Hirshfeld surface analyses of these supramolecular assemblies have been performed. The π-systems of protonated pyridine and imidazole rings play a pivotal role in establishing the noncovalent π•••π type supramolecular interactions in both the crystals, and the π-system-directed associations certainly assist in forming the 3D supramolecular architectures of ITP-Cl and ITP-Br in the solid state. Most intriguingly, the supramolecular association of ITP-Cl uniquely stabilizes the cationic unit of hydroxonium hydrate (i.e., H 5 O 2 + ) in the solid state, and such solid-state stabilization of H 5 O 2 + by the imidazole-connected terpyridine-based system is one of the pioneering challenges in crystal engineering. Distinctly, the hydrogen-bonded cluster-like assembly of H 5 O 2 + and Cl − has been observed in the ITP-Cl system through hydrogen donor−acceptor balance. Subsequently, a special drive has been endeavored to unveil the semiconducting features, including the charge transport property and photoresponsive behavior, of these synthesized ITP-Cl and ITP-Br-based devices. Fascinatingly, the chloride-mediated ITP-Cl-based device shows remarkably higher electrical conductivity with respect to the ITP-Br-based device under photoirradiation conditions, and this implies the tuning effect of different halides toward the applicability of thin-film-based device performance. The device efficiency-based experimental outcomes have been rationalized through a density functional theory-level analysis.