Organic superalkalis are carbon-based species possessing lower ionization energy than alkali atom. In the quest for new organic superalkalis, we study the MC 6 Li 6 (M = Li, Na, and K) complexes and their cations by decorating hexalithiobenzene with an alkali atom using density functional theory. All MC 6 Li 6 complexes are planar and stable against dissociation into M + C 6 Li 6 fragments, irrespective of their charge. These complexes are stabilized by charge transfer from M to C 6 Li 6 , although the back-donation of charges tends to destabilize neutral species. Furthermore, their degree of aromaticity increases monotonically from M = Li to K, unlike MC 6 Li 6 + cations, which are not aromatic as suggested by their NICS values. The adiabatic ionization energies of MC 6 Li 6 (3.08-3.22 eV) and vertical electron affinities of MC 6 Li 6 + (3.04-3.15 eV) suggest that MC 6 Li 6 species form a new series of aromatic superalkalis. The variation of the ionization energy of MC 6 Li 6 is found to be in accordance with the NICS values of MC 6 Li 6 + . The superalkali nature of MC 6 Li 6 and its relation withNICS values are explained on the basis of the positive charge delocalization. We believe that these species will not only enrich the aromatic superalkalis but also their possible applications will be explored.