Abstract Quercetin (Q) as a pentahydroxy flavonoid, has three possible chelating sites competing in complexation processes. 1H and 13C MAS NMR spectra were recorded for solid quercetin and its Al(III) complex (AlQ). 1H MAS spectrum of quercetin shows a broad resonance at ca. 12ppm that confirms the existence of intramolecular C5OH … OC4 hydrogen bond. Such a signal is absent in the spectrum of AlQ, which is in accordance with other spectroscopic data and the suggested model for the solid-state structure of the complex. DFT GIAO calculations were used to verify the experimental 13C CPMAS NMR data and to suggest the best model structure for the complex AlQ. The calculated shielding constants for different conformers of isolated quercetin molecules, quercetin trimer as taken from the X-ray data, and different model structures for possible Al(III) complexes were compared with the 13C CPMAS NMR experimental values. The results demonstrate the importance of intermolecular interactions when dealing with structures in solid state and the successful application of the combined DFT GIAO and 13C CPMAS NMR approach. All data confirm that the chelating site of Q in the solid complex AlQ involves the deprotonated C5OH and the C4O groups at ring C, in contrast to the available studies performed in solution.