Treatment of fac-[Rh(apt)(3)] (apt = 3-aminopropanethiolate) with [Cu(CH3CN)(4)](+) in a 2: 3 ratio in water gave a (Cu3Rh2III)-Rh-I pentanuclear complex ([1(apt)](3+)), in which two octahedral fac-[Rh(apt)(3)] units are linked by three linear Cu-I ions through sulfur bridges. Complex [1(apt)](3+) was oxidized to produce a (CuCuII)-Cu-I-Rh2(III) tetranuclear complex, in which two fac-[Rh(apt)(3)] units are linked by linear Cu-I and square-planar Cu-II ions. The structure and properties of [1(apt)](3+) were compared with those of the corresponding (Cu3Rh2III)-Rh-I complex with 2-aminoethanethiolate.