The self-assembly of metallosupramolecules from reactions of flexible 2-pyridyl ligands and silver salts is described. When 1,3-bis(2-pyridyl)propane (L-1), tris[(2-pyridyl)methyl]methane (L-2), and 1,3-bis(2-pyridyl)-2-tolylpropane (L-3) are used in combination with silver ions, novel discrete metallocyclic complexes are formed in crystals. Moreover, the self-assembly of 1,3-bis(2-pyridyl)-2-phenylpropane (L-4) with silver nitrate yields a coordination polymer. The examination of its solution shows that this coordination polymer is formed via the solution-based discrete metallocyclic species.