The reaction of WSCl₄ and Me₃SiS₂CNEt₂ in tetrahydrofuran produces a green solid which yields WS(S2)(S₂CNEt₂)₂, WO(S₂)(S₂CNEt₂)₂ and syn-W₂O₂( µ-S)₂(S₂CNEt₂)₂ upon exposure to oxygen. Crystals of syn-W₂O₂( µ-S)₂(S₂CNEt₂)₂ are monoclinic and belong to space group C2/c with a 33.880(4), b 7.012(1), c 18.072(1) Å ,β 105.94(1)º and Z 8. Refinement on 2651 data measured with Cu K α: radiation converged at R 0.070. The complex possesses a syn-[W₂O₂(µ-S)₂]₂⁺ core with a W-W bond [2.808(1) Å ] and two terminal W-O bonds [1.66(2) and 1.68(2) Å ]. The W-S(bridging) bond distances are in the range 2.319(5)-2.3346) Å Each of the square-pyramidal tungsten atoms is further coordinated to a bidentate dithiocarbamate ligand with W-S bond distances ranging from 2.447(6) to 2.459(5) Å .