AbstractReactions of (NEt4)2[Re(CO)3Br3] with N‐heterocyclic thiols such as 2‐mercaptobenzimidazole (H2Sbenzim), 2‐mercaptothiazoline (HSthiaz), or 5‐mercapto‐1‐methyltetrazole (HSmetetraz) give rhenium(I) complexes of various compositions: (NEt4)[Re(CO)3Br2(H2Sbenzim)], [Re(CO)3(HSthiaz)3]Br, and (NEt4)[Re2(CO)6(μ‐S‐Smetetraz‐κS)(μ‐N,S‐Smetetraz‐κS,N)2]. Corresponding reactions with 2‐mercaptopyridine (HSpy) and bis(2‐pyridine)diselenide [(Sepy)2] did not give defined products in reasonable yields, whereas [Re(CO)5Br] reacts with HSpy and (Sepy)2 with formation of [Re(CO)3(HSpy)3]Br and [Re2(CO)6(Sepy)2], respectively. All reactions were performed without the addition of a supporting base and the sulfur‐containing organic ligands are coordinated in their thione forms with the exception of Smetetraz– in its μS‐bridging coordination mode in (NEt4)[Re2(CO)6(μ‐S‐Smetetraz‐κS)(μ‐N,S‐Smetetraz‐κS,N)2], which can be regarded as thiolate. The bonding mode of the selenium containing ligands in the dimeric compound [Re2(CO)6(Sepy)2] (C–Se distance: 1.93 Å) can also best be described as selenolate. The products are stable on air at an ambient temperature. They were studied spectroscopically and by X‐ray diffraction.