A new class of metal sandwich complexes of silver derived from silver(I) perchlorate and fluoranthene (L-1), benzo[ghi]perylene (L-2), [2,2]paracyclophane (L-3), and decacyclene (L-4) was prepared. The idea behind the use of polycyclic aromatic compounds as an alternative approach for construction of organometallic sandwich systems is to combine the plasticity of the metal ion and planarity and coordinative diversity of the hydrocarbons. Structural studies by single-crystal X-ray diffraction have shown that all compounds contain extended one- to three-dimensional structures in which several metal atoms are sandwiched between two fused polycyclic systems. While complex 1, [Ag-3(L-1)(2)(ClO4)(3)], exists in the solid state as a two-dimensional W-type architecture in which AgClO4 layers are separated by two sheets of hydrocarbon, complex 2, [Ag(L-2)(ClO4)](4). toluene, contains two double-decker polymeric chains coupled via extensive aromatic pi-pi stackings. Pillared brick sandwiched framework was observed in 3, [Ag(L-3)(ClO4)], whereas the multidecker sandwich complex 4, [Ag-2(L-3)(ClO4)(2)(benzene)], is reminiscent of ladder. The structure of L-1 has been redetermined and that of L-2 reported; the structural data are used for discussion of the silver-pi interactions. The electrochemical behavior and ESR spectra are consistent with formation of the organic radical species in the system. The present findings may represent an alternative approach for predesigning the multilayered systems in organometallic chemistry.