The reaction offac(S)-[RhIII(aet)3] (aet = 2-aminoethanethiolate) with [AuIIICl4]−in water gave an S-bridged pentanuclear complex [AuI3{RhIII-(aet)3}2]3+(1), accompanied by the spontaneous reduction of AuIIIto AuI. The crystal structure of1(NO3)3·4H2O was determined by X-ray crystallography. In1two octahedralfac(S)-[Rh(aet)3] units are linked by three linear AuIatoms to form a trigonal-bipyramid-type RhIII2AuI3pentanuclear structure with an averaged AuI-AuIdistance of 3.083(5) Å. The two RhIII2AuI3cations contact with each other through one AuI-AuIinteraction with a distance of 3.311(3) Å. The optically active δδ-1was derived from ΔΔΔΔ-[Zn3(OH){Rh(aet)3}4]5+by reacting with [AuCl4]−in water.