The structures of tris(8-hydroxyquinoline) aluminum(III) (Alq3) in the different polymorphs, α-, γ-, and δ-Alq3, and in the amorphous state, amo-Alq3, have been analyzed by solid-state 27Al nuclear magnetic resonance (NMR). The local structures of α- and amo-Alq3 are found to be similar; both samples are composed of the meridional isomer and are locally disordered. No evidence of the existence of the facial isomer is found even for amo-Alq3. In contrast, the isomeric states of γ- and δ-Alq3 are facial. The 27Al NMR spectrum of δ-Alq3 is influenced by intermolecular interactions, whereas that of γ-Alq3 is determined only by a single facial Alq3 molecule, suggesting that intermolecular interactions are negligible for γ-Alq3. This result is closely related to the experimentally observed good solubility of γ-Alq3. Density functional theory (DFT) calculations support the identification of the isomeric state and the effect of the intermolecular interactions. A clear correlation between the isomeric state and the fluorescence wavelength is found, indicating that the isomeric state of Alq3 is a crucial factor for the light-emitting properties.