The first binary hexameric silver(I) pyrazolate (Ag(6)pz(6)) has been prepared, and X-ray analysis demonstrated that it takes a rare figure-eight shape (pz(-) = deprotonated tert-butyl 3,5-diphenyl-1H-pyrazole-4-carboxylate). The hexamer can be easily converted to its tetrameric isomer (Ag(4)pz(4)) by recrystallization from ether. On the basis of the IHNMR and mass spectrometry measurements, it is conjectured that the hexamer, after dissolving in CHCl3, quickly achieves equilibrium with Ag(4)pz(4) and Ag(3)pz(3), with the equilibrium lying far to the side of smaller rings.