Aromaticity is one of the important chemical properties of aromatic compounds. Clarifying the aromaticity of a clearly ring?conjugated system is crucial for understanding the chemical reactivity and stability of the system. A detailed study of the aromaticity, one?photon absorption (OPA), two?photon absorption (TPA) spectra, and electron transfer properties of Kekulene was carried out through quantum chemical calculations and wave function analysis. The aromaticity of different benzene rings in the molecule was quantitatively analyzed through multicenter bond indices and AV1245 indices. The aromaticity of Kekulene was studied through various methods such as electron localization function (ELF), localized orbital locator (LOL), magnetic susceptibility current, and isotropic chemical shielding surface (ICSS). The electron transfer processes of OPA and TPA transitions were visualized through charge difference density (CDD) analysis. The results showed that the aromaticity of rings 1 and 2 was significantly stronger than that of rings 3 and 4. The π electrons of ELF and LOL can be highly delocalized on both sides of the first ring and form a loop. The OPA spectrum has excited states with higher transition dipole moments, which are more likely to become intermediate states in the TPA process. The research results can provide effective theoretical methods and application approaches for the aromaticity of different systems.