The complexes fac-[Re(CO)3BrPh2P(S)(CH2)nP(S)Ph2}] [1a, n = 1; 2a, n = 2; 3a, n = 3] and [Re2(CO)8Br2μ- Ph2P(S)(CH2)nP(S)Ph2}] [1b, n = 1; 2b, n = 2; 3b, n = 3] have been prepared by the photochemical reaction of Re(CO)5Br with Ph2P(S)(CH2)nP(S)Ph2. The products have been characterized by elemental analysis, mass spectroscopy, FT-IR and 31 P-[1H]-NMR spectrometry. The results suggest cis-chelate bidentate coordination of the ligand in fac-1a - 3a and cis-bridging bidentate coordination of the ligand between two metals in 1b - 3b.