The title compound, [V(2)Cl(4)O(2)(CH(3)CN)(4)], is a centrosymmetric dinuclear V(IV) complex associated with four mol-ecules of acetonitrile. The coordination around both V(IV) atoms is essentially square-planar, involving three Cl atoms and one O atom [maximum deviation = 0.017 (3) Å for the O atom]. The augmented octahedral coordination of the metal atom is completed by the N atoms of acetonitrile ligands. The V(IV) atoms are linked by two Cl atoms, acting as bridging atoms. The crystal studied was a non-merohedral twin with a ratio of the two twin components of 0.8200 (3):0.1800 (3). Although Cl and O atoms are present as potential acceptors in the title compound, no hydrogen bonds were observed in the crystal structure.