As a continuation of the study on the construction of the multidecker aromatic compounds with pi-pi interactions, the anthracene derivatives 9,10-dimethylanthracene (dman), 9,10-diphenylanthracene (dpan), and 7,12-dimethylbenz[a]anthracene (dmban) have been studied toward complexation with the silver(l) ion. The crystal structures of [Ag(dman)(0.5)(p-xylene)(ClO4)], [Ag-2(dpan)(0.5)(C6H6)(0.5)(CF3SO3)(2)], and [Ag-2(dmban)(2)(ClO4)(2)](p-xylene), together with the metal-free ligand dpan, have been determined by single-crystal X-ray diffraction. These pi-electron-rich aromatic compounds are found to have great promise as an approach to the effective! self-assembly of high nuclearity in a multilayer fashion.