By means of density functional theory, a hexanuclear sandwich complex [18]annulene-Li-6-[18]annulene which consists of a central Li-6 hexagon ring and large face-capping ligands, [18]annulene, is designed and investigated. The large interaction energy and HOMO-LUMO gap suggest that this novel charge-separated complex is highly stable and may be experimentally synthesized. In addition, the stability found in the [18]annulene-Li-6-[18]annulene complex extends to multidecker sandwich clusters (Li-6)(n)([18]annulene)(n+1) (n = 2-3). The energy gain upon addition of a [18]annulene-Li-6 unit to (Li-6)(n-1)([18]annulene)(n) is pretty large (96.97-98.22 kcal/mol), indicating that even larger multideckers will also be very stable. Similar to ferrocene, such a hexanuclear sandwich complex could be considered as a versatile building block to find potential applications in different areas of chemistry, such as nanoscience and material science.