Reduction-substitution reactions between high valent [ReOCl 4 ] [NBu 4 ] or [ReNCl 4 ] [NBu 4 ] complexes and the phenyldithiocarboxylate piperidinium salt lead to a novel rhenium(III) complex with mixed coordination sphere. The structure of this compound [Re(S 3 CPh) 2 (S 2 CPh)], containing two trithioper xybenzoate and one dithiobenzoate ligands, has been elucidated by NMR, mass spectrometry and X-ray diffraction analysis.