Treatment of the Rh(III) complex [Tp∗Rh(SPh) 2 (MeCN)] (1) with a series of late transition metal complexes resulted in the formations of thiolate-bridged di- and trinuclear complexes, which include the Rh(III)–Rh(I) complexes, [Tp∗RhCl(μ-SPh) 2 Rh(cod)] (2) and [Tp∗RhCl(μ-SPh) 2 Rh(PPh 3 ) 2 ], the Rh(III)–Pd(II) complexes, [Tp∗RhCl(μ-SPh) 2 Pd(η 3 -C 3 H 5 )] (4), [{Tp∗Rh(MeCN)}(μ-SPh) 2 PdCl 2 ] (5), and [{Tp∗RhCl(μ-SPh) 2 } 2 Pd] (6), and the Rh(III)–Pt(II) complex [{Tp∗RhCl(μ-SPh) 2 } 2 Pt] (7). Early-late transition metal complexes containing the Rh(III)–Re(I) and Rh(III)–Mo(0) metal centers, [Tp∗RhCl(μ-SPh) 2 Re(CO) 4 ] and [{Tp∗Rh(CO)}(μ-SPh) 2 Mo(CO) 4 ] were also prepared from 1. The X-ray analysis has been carried out to confirm the structures for 2, 4, 5, 6, and 7.