For the purpose of investigating the coordination behavior of the sterically congested alkenes and exploring the possibility of cofacial complexation in the polycyclic aromatic system for formation of extended polymeric networks, tetraphenylethylene (tphe) and 1,1,4,4-tetraphenyl-1,3-butadiene (tphb) have been studied with regard to their complexation with a silver(I) ion. The crystal structures of [Ag(tphe)(ClO4)(p-xylene)], [Ag-2(tphe)(ClO4)(2)], [Ag-4(tphe)(CF3SO3)(4)], [Ag-2(tphb)(ClO4)(2)], and [Ag-2(tphb)(CF3SO3)(2)], together with the metal-free ligands tphe and tphb, have been determined by single-crystal X-ray diffraction. The pi -electron-rich cleft in organic components is found to offer a potential site for complexation, which can be utilized to generate an interesting array of organometallic compounds with one- and two-dimensional frameworks.