A series of SNn mixed‐donor ligands [n = 2: H2NC2H4SCH2‐2‐pyridyl (2‐NSpy) (1a), H2NC2H4SCH2‐4‐pyridyl (4‐NSpy) (1b), n = 3: 2‐pyridylCH2NHC2H4SCH2‐2‐pyridyl (2‐pyNSpy) (2), n = 4: (2‐pyridylCH2)2NC2H4SCH2‐2‐pyridyl (2‐py2NSpy) (3)] was utilized to support homo‐ and heterodinuclear complexes including Cp*MIII units (M = Rh, Ir; Cp* = pentamethylcyclopentadienyl). Reactions of [Cp*MCl2]2 with 2‐pyNSpy (2), 2‐py2NSpy (3), and 4‐NSpy (1b) afforded homodinulear complexes, [(Cp*MCl)(2‐pyNSpy)(Cp*MCl)](PF6)2 [M = Rh (5a), Ir (5b)], [(Cp*M)(2‐py2NSpy)(Cp*MCl)](PF6)3 [M = Rh (6a), Ir (6b)], [(Cp*MCl)(4‐NSpy)(Cp*MCl2)]Cl [M = Rh (8a), Ir (8b)]. Heterodinuclear complexes [(Cp*MCl)(4‐NSpy)(Cp*M′Cl2)]Cl [M, M′ = Rh, Ir (8c), Ir, Rh (8d)] were prepared using mononuclear complexes [(Cp*MCl)(4‐NSpy)]Cl [M = Rh (7a), Ir (7b)] reacted with [Cp*MCl2]2 (M = Ir, Rh), respectively. Complexes 5–8 were characterized by X‐ray crystallography to determine the configurations around the M, M′, S, and N centers. The solid‐state structures of 6 are retained in acetonitrile solution whereas four diastereomers are generated in the case of 5 due to low stereoselectivity around the coordinated amine nitrogen atom, in contrast to the sulfur atom. Heterodinuclear complexes 8c,d are unstable in solution at 55 °C, readily affording mixtures of 8a–d via intra‐ and intermolecular coordination‐site‐exchange reactions of Cp*M fragments between the SN moiety and the py site. In order to evaluate the selectivity of Cp*M fragments for the SN and py coordination sites, several competitive reactions of [Cp*MCl2]2 (M = Rh, Ir) with H2NC2H4SCH2C6H5 (NSph) (4) and/or 4‐methylpyridine (4‐Mepy) were carried out to demonstrate predominant formation of iridium complexes 9b and 10b among [(Cp*MCl)(NSph)]Cl [M = Rh (9a), Ir (9b)] and [(Cp*MCl)(4‐Mepy)]Cl [M = Rh (10a), Ir (10b)]. These reactions indicated higher affinity of the Cp*Ir fragment to both the NS and py sites relative to the rhodium analogue.