The designed synthesis and structural characterization of two metal cluster-centered metallosupramolecular architectures are reported. In complex [(CF3SO3)Ag-4((BuC)-Bu-t C)(Py8)](CF3SO3)(2) (1) and [(CF3SO3)Ag-4{C C-(m-C6H4)-C C-(m-C6H4)-C C-(m-C6H4) -C C}Ag-4(CF3SO3)(Py8)(2)] (CF3SO3)(4) (2), organic acetylide ligands are utilized to induce the formation of polynuclear silver aggregates, which are encapsulated into the central cavity of the neutral macrocyclic compound azacalix[8]pyridine (Py8). The tetrasilver cluster centered [2]- and [3]-pseudo-rotaxane structures are obtained and fully characterized by X-ray crystallography, ESI mass spectrometry, and H-1 NMR spectroscopy.