Lewis acids and Lewis adducts are widely used in the chemical industry because of their high catalytic activity. Their precise geometrical description and understanding of their electronic structure are a crucial step for targeted synthesis and specific use. Herein, we present an experimental/computational strategy based on a solidstate NMR crystallographic approach allowing for detailed structural characterization of a wide range of organoaluminum compounds considerably differing in their chemical constitution. In particular, we focus on the precise measurement and subsequent quantumchemical analysis of many different Al-27 NMR resonances in the extremely broad range of quadrupolar coupling constants from 1 to 50 MHz. In this regard, we have optimized an experimental strategy combining a range of static as well as magic angle spinning experiments allowing reliable detection of the entire set of aluminum sites present in trimesitylaluminum (AlMes(3)) reaction products. In this way, we have spectroscopically resolved six different products in the resulting polycrystalline mixture. All Al-27 NMR resonances are precisely recorded and comprehensively analyzed by a quantum-chemical approach. Interestingly, in some cases the recorded Al-27 solid-state NMR spectra show unexpected quadrupolar coupling constant values reaching up to ca. 30 MHz, which are attributed to tetra-coordinated aluminum species (Lewis adducts with trigonal pyramidal geometry). The cause of this unusual behavior is explored by analyzing the natural bond orbitals and complexation energies. The linear correlation between the quadrupolar coupling constant value and the nature of bonds in the Lewis adducts is revealed. Moreover, the Al-27 NMR data are shown to be sensitive to the geometry of the tetra-coordinated organoaluminum species. Our findings thus provide a viable approach for the direct identification of Lewis acids and Lewis adducts, not only in the investigated multicomponent organoaluminum compounds but also in inorganic zeolites featuring catalytically active trigonal (Al-III) and strongly perturbed Al-IV sites.