The half-sandwich rhenium(VII) complex (η5-C5Me5)ReO3 (1; Me = CH3) undergoes reduction with thiophenol giving the rhenium(V) condensation product (η5-C5Me5)Re(O)(SC6H5)2 (2a) in high yield. However, toluene-3,4-dithiol reacts only slowly with 1, with traces of the fully substituted rhenium(V) species (η5-C5Me5)Re(1,2-S2C6H3-4-CH3)2 (3a) being formed. The related N,S-chelating ligand 2-aminothiophenol forms the amido derivative (η5-C5Me5)Re[1,2-S(HN)C6H4]2 (3b) in good yield. Compounds 3a and 3b are also accessible by two alternative routes: (i) from (η5-C5Me5)Re(O)Cl2 (4) and the corresponding thiols in the course of two-step substitution/condensation reactions via the intermediates (η5-C5Me5)Re(O)(1,2-S2C6H3-4-CH3) (2b) and (η5-C5Me5)Re(O)[1,2-S(HN)C6H4] (2c), respectively; (ii) from the tetrachloro complex (η5-C5Me5)ReCl4 (5) and two equivalents of the respective ligands. Employing a 1 : 1 stoichiometry, reaction of (η5-C5Me4Et)ReCl4 (5′; Et = C2H5) with 2-aminothiophenol yields the amidothiophenolato(N,S) complex of formula (η5-C5Me4Et)Re[1,2-S(HN)C6H4]Cl2 (6′). The solid-state structure of the bis(dithiolato)rhenium(V) complex 3a was determined by means of X-ray diffraction techniques. The core geometry around the rhenium is almost perfectly square pyramidal, with the five-membered ring ligand occupying the apical position (centroid π-coordination), while the four sulphur atoms define the basal plane. The relatively short distances between the interligand sulphur atoms (297-301 pm) are compatible with possible bonding interactions, e.g. partial disulphide character.