The gold(I) selenolate compound [Au-2(SePh)(2)(mu-dppf)] (dppf = 1,1'-bis(diphenylphosphino)ferrocene) has been prepared by reaction of [Au2Cl2(mu-dppf)] with PhSeSiMe3 in a molar ratio 1:2. This complex reacts with gold(I) or gold(III) derivatives to give polynuclear gold(I)-gold(I) or gold(I)-gold(III) complexes of the type [Au-4(mu-SePh)(2)-(PPh3)(2)(mu-dppf)](OTf)(2), [Au-3(C6F5)(3)(mu-SePh)(2)(mu-dppf)], or [Au-4(C6F5)(6)(mu-SePh)(2)(mu-dppf)], with bridging selenolate ligands. The reaction of [Au-2(SePh)(2)(mu-dppf)] with 1 equiv of AgOTf leads to the formation of the insoluble Ag(SePh) and the compound [Au-2(mu-SePh)(mu-dppf)]OTf. The complexes [Au-4(C6F5)(6)(mu-SePh)(2)(mu-dppf)] and [Amu(2)(mu-SePh)(mu-dppf)]OTf (two different solvates) have been characterized by X-ray diffraction studies and show the presence of weak gold(I)-gold(III) interactions in the former and intra- and intermolecular gold(I)-gold(I) interactions in the later.