The choice of solvent plays a crucial role in determining the formation of various polymorphs, 10 hydrates, and solvates of cocrystals, as it subtly modulates intermolecular interactions during crystallization. This influence is particularly evident in the case of cocrystal CA•7, where three distinct polymorphs have been identified: two polar phases (Polymorph I and Polymorph II) and one nonpolar phase (Polymorph III). Notably, all three phases are free of trapped solvent molecules within their crystal structures. Predicting the characteristics of different polymorphs based solely on 15 the Eg proves inadequate. This limitation is evident in the force plot for the three polymorphs of CA•7 (Supplementary Fig. ), where the feature B_HOMO_LUMO predicts polar cocrystals across all phases. Despite sharing the same composition, these polymorphs exhibit notable differences in unit cell parameters and molecular packing (Supplementary Fig. ). In the structure of Polymorph I, the cocrystal forms zero-dimensional hydrogen-bonding networks with CA, Here, the molecular plane of CA is nearly parallel to that of PHEN, with a dihedral angle of 1.50°. In contrast, Polymorph III, the nonpolar phase, adopts a distinct packing arrangement, where two molecules of PHEN and two molecules of CA in the asymmetric unit form a more complex pair. This arrangement exhibits weaker orbital interactions and exchange energy between the molecules, as indicated by energy decomposition analysis (EDA) .