The dinuclear molecule of the title complex, [VOCl{μ-OC(Me)₂P(iPr)₂-κ²O}]₂or [V₂(C₉H₂₀O₂P)₂Cl₂O₂], which was obtained due to an unexpected oxidation reaction, is centrosymmetric, with the inversion centre located in the middle of the central V₂O₂core. These core O atoms arise from the symmetry-related 2-(diisopropylphosphoryl)propan-2-olate dianions. The V^IVatom is additionally bonded to one terminal Cl ligand, the second O atom of the dianion and double bonded to a vanadyl O atom, leading to an overall distorted square-pyramidal VO₄Cl coordination polyhedron with the vanadyl O atom as the apex. An intramolecular C—H...Cl contact helps to establish the molecular configuration. In the crystal, molecules are stacked in rows parallel to [001] and are linked by C—H...Cl contacts to form chains running in the same direction.