The reactions of fac(S)-[M(aet)(3)] (M = Rh-III, Ir-III; aet = 2-aminoethanethiolate) with RuCl3• 3H(2)O in water gave trinuclear complexes, &UDelta;&ULambda;-, &UDelta;/&ULambda;-[Ru{Rh(aet}(3))(2)](3+) (1a, 1b.) and &UDelta;&ULambda;-, &UDelta;&UDelta;/&ULambda;&ULambda;-[Ru{Ir(aet)(3)}(2)](3+) (2a, 2b). The crystal structure of 2a(NO3)(3)• 3H(2)O revealed that the central Ru-III ion is coordinated by six S atoms from two fac(S)-[Ir(aet)(3)] units in an octahedral geometry, forming a linear-type S-bridged trinuclear structure. It was found that the UV-Visible (UV-Vis) spectral patterns of all complexes depend upon the terminal fac(S)-[M(aet)(3)] units. In the electro- and spectroelectrochemistry of these complexes, the Ir trinuclear complex showed a reversible [Ru{Ir(aet)(3)}(2)](3+/4+) redox process.