The missing member of the series Tp*ME(S2CNEt2) (M = Mo, W; E = O, S), namely Tp*WO(S2CNEt2), has been synthesized by oxygen-atom transfer from pyridine N-oxide to Tp*W(S2CNEt2)(CO)2. The air-stable, blue-purple complex was characterized by microanalysis, mass spectrometry (m/z 645 (100%), [M]+), cyclic voltammetry, and IR and 1H NMR spectroscopy. Solutions of the complex are dichroic and solvatochromic. The X-ray crystal structure of the complex revealed a six-coordinate, distorted octahedral complex with axial oxo (W = O 1.680(5) Å), ‘equatorial’ dithiocarbamate (W—S 2.3962(17) and 2.4102(17) Å), and facial tridentate Tp* ligands. The synthesis and characterization of Tp*WCl3 are also reported.