The reaction of Cp2*Mo2S4I2(Cp* = eta(5)-C5Me5) with two equivalents of NaSR (R = Me, (i)Pr, (t)Bu, Ph) gives the complexes Cp2*Mo2(mu,eta(1)-SSR)2(mu-S)2 (2a-d) in nearly quantitative yields. The compounds have been investigated spectroscopically and in the case of R = Ph (2d) by means of X-ray diffraction analysis. The results show the presence of two eta(1)-PhSS- bridges (d(s-s) 2.139(2) angstrom) and that exclusively the trans-isomer is formed. All sulfur atoms lie in one plane perpendicular to the Mo-Mo axis and bisecting it.