Crystals of 4′-(isoquinolin-4-yl)-4,2′:6′,4″-terpyridine (iqtp), C₂₄H₁₆N₄, grown from an ethanol solution, undergo a reversible first-order single-crystal to single-crystal phase transition at T_c in the range 273-275 K, from a disordered higher-temperature phase [form (I)] in the space group P2₁/c, with one single molecule in the asymmetric unit, to an ordered lower-temperature one [form (II)] in the space group P2₁/n, with two independent molecules in the asymmetric unit. There is a group-subgroup relationship linking (I)-(II), due to cell doubling and the disappearance of a number of symmetry operations. In addition to X-ray diffraction, the transition has been monitored by Raman spectroscopy and differential scanning calorimetry, the latter disclosing an enthalpy change of 0.72 (6) kJ mol^-1. Variations of the unit-cell parameters with temperature between 170 and 293 K are presented. The evolution of diffraction spots in the vicinity of the transition temperature shows the coexistence of both phases, confirming the first-order character of the transition. Structural details of both phases are analyzed and intermolecular interactions compared in order to investigate the mechanism of the phase transition. A three-dimensional Hirshfeld surface analysis was performed to corroborate the significant changes in the intermolecular features.