By treatment of the polymeric species [AuTI(C6Cl5)(2)](n) with ketones or with acetylacetone and 4,4'-bipyridine, the new tetranuclear complexes [Au2Tl2(C6Cl5)(4)]center dot(L = PhMeC=O, acacH) or [Au2Tl2(C6Cl5)(4)(bipy)]center dot(acacH) have been prepared. Their crystal structures have been determined by X-ray diffraction methods and they all present a central Au2Tl2 core formed via one (TlTI)-T-... and four (AuTl)-Tl-... unsupported interactions resulting in a loosely bound butterfly cluster. These complexes are strongly luminescent in both the solid state and solution showing an optical behavior in agreement with the maintenance of the (TITI)-T-... contact even in solution.