Abstract WOCl 4 reacts with (Me 3Si) 2O and excess THF to give [WO 2Cl 2(THF)] 4 ( 1), a new tetrameric tungsten(VI)-oxo complex, which was characterized and crystal structure was determined by X-ray crystallography. Complex 1 has a roughly square planar tetranuclear structure bridged by μ-oxo ligands. Each tungsten atom is coordinated by two bridging oxygens, one terminal oxygen, two “axial” chlorine atoms and one “equatorial” O-bonded THF ligand. One of the two μ-oxo ligands is similar to the terminal oxygen atom and the other one is similar to the coordinated oxygen atom of the THF ligand, respectively, which confirmed a previous proposal. Four WO 3Cl 2(THF) octahedral are associated by sharing corners. Complex 1 is different from three known tetrameric tungsten analogues in its structural arrangement and properties.