Three cocrystals of acridine with 2,7-dihydroxynaphthalene (Ia and Ib) in two different polymorphs and 1,5-dihydroxynaphthalene (II) have been synthesized and characterized by single crystal x-ray diffraction method. Two polymorphs of acridine,2,7-dihydroxynaphthalene cocrystal crystallizes in same sapcegroup P-1 with different unit-cell parameters. In (Ia) the O‒H group form a syn-anti conformation whereas in (Ib) the O‒H group form an anti-anti conformation leads to the polymorphic structure of acridine, 2,7-dihydroxynaphthalene. This study reveals that the influence of π…π and C‒H…π interactions in the formation of one-, two-, and three-dimensional supramolecular frameworks when the classical hydrogen bonds such as O‒H…N and C‒H…O are limited to discrete motifs. The acridine molecules form continuous π…π stacking in the crystal structure of (Ia) and discrete π…π stacking in the crystal structure of (Ib) and (II). The conformational flexibility of the substituted hydroxy group has an influence in the supramolecular frameworks of the three-dimensional crystal structure. The intermolecular interaction energy calculation between the molecular pairs has been carried out to study the strength of the interaction and its dependence on the geometrical parameters.