A series of four photoluminescent binuclear copper(I) compounds bearing phosphorus and sulfur donor atom ligands have been synthesized from reactions of copper(I) halides with the diphosphane dppe [1,2-bis(diphenylphoshino)ethane] and the anions of three different N-heterocyclic thiols, namely 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-1H-tetrazole-5-thiol and ethyl 2-thiouracil-5-carboxylate. Depending on the nature of the N-heterocyclic thiol, the resulting compounds adopt two different structural motifs, having either a dppebridged core, that is, [Cu 2 (κ-S-thiolate) 2 (dppe) 2 (μ-dppe)], or a bis(thiolate)-bridged core, that is, [Cu 2 (μ-S-thiolate) 2 (dppe) 2 ], with a Cu 2 (μ-S) 2 cluster-type core. The stabilization of the latter type of structure is rationalized by the presence of intramolecular hydrogen-bonding interactions developed between two bridging N-heterocyclic thiolate ligands positioned at the same side of the Cu 2 (μ-S) 2 core, which lead to short Cu···Cu interactions (ca. 2.6 Å), as it is evidenced by X-ray crystallography stud- [a]