Thiolato-bridged hexanuclear mixed-valence complex, [(Cu3Cu3II)-Cu-I(apampt)(3)Cl-6] (Hapampt = 1-[(3-aminopropyl)amino]-2-methylpropane-2-thiol), has been synthesized and characterized by X-ray crystallography. Spectroscopic data as well as structural features support a localized mixed-valence state. Magnetic susceptibility data show that a strong anti ferromagnetic interaction is operating between the Cull ions.