Nitrogen clusters have been intensively studied for their potential application as high-energy density materials, but a six-membered nitrogen ring (N6) was not found to be stable and aromatic. To explore the possibility of inducing an aromatic N6 ring via cation-pi interaction, quantum chemistry calculations were performed on the systems of Ca2N6, CaN6, CaN6(2-), N6, and N6(4-) at the B3LYP/6-311+G level. The optimized geometries reveal that the planar structure of the N6 ring is stable only in the Ca2N6 complex. The computed NBO and CHelpG charges demonstrate that the planar N6 moiety in the Ca2N6 complex is almost a 10pi-electron system. The predicted nucleus-independent chemical shift (NICS) values demonstrate that the N6 moiety is aromatic in comparison with the NICS values of benzene. The estimated enthalpy of formation for the Ca2N6 complex is 100.4 kcal/mol for the reaction of 2Ca and 3N2. The binding energy between the Ca2+ cation and the N6(4-) moiety is -1928.8 kcal/mol, with electrostatic interaction serving as the predominant component. When all the calculated results are taken into account, including the planar structure, 10pi-electron system, identical bond length, and negative NICS value of the N6(4-) moiety in the Ca2N6 complex, it is deduced that the alkaline earth metal Ca is capable of inducing an aromatic N6 ring through the cation-pi interaction formed by electron transfer from the Ca atom to the N6 ring.