The first comprehensive theoretical analysis of recently synthesized sandwich-like aggregates of highly reduced corannulene, in which two bowl-shaped fragments are bound together by six metal cations (here, alkali metals Li and K), was accomplished and allowed one to unambiguously assign the nature of the new record 7Li-NMR chemical shift of ~ − 25 ppm, experimentally observed in these systems. This record chemical shift corresponds to the central Li+ sandwiched between two 5-membered rings of tetra-reduced corannulene (Li-1). For comparison, the chemical shielding tensor was also considered for the neighboring lithium center, which occupies position between two 6-membered rings of [(C20H104−)(Li3K3)6+(C20H104−)]2− (Li-2). The chemical shift for this cation was calculated to be equal to ~ − 8 to 9 ppm and lies within a standard window of the 7Li-NMR technique. A significant anisotropy of the shielding tensor in zz-direction was found for both Li-1 and Li-2 centers. Subsequent MO-by-MO analysis revealed the contribution from π-orbitals of corannulenes to be the main reason for the difference between chemical shifts calculated for these lithium centers. Further detailed analysis of molecular orbitals revealed that the bowl fragments in sandwich-like aggregates of highly reduced corannulene are strongly electronically coupled. Moreover, the 7Li-NMR signal measured for the Li-1 center can now naturally be used as the very sensitive probe of the strength of such coupling.