The structure of the dimeric oxomethoxovanadium(V) complex, [V2(CH3O)2(C11H11N3O3)2] or [VO(μ-OMe)(L)]2 (1), with N′-[3-(hydroxyimino)-butan-2-ylidene]benzohydrazide (H2 L, where 2 Hs represent the dissociable oxime and amide protons) is reported. The oximate functionality can coordinate through either the O or the N atom. In the present complex, it is coordinated through the O atom. Here, methoxo groups bridge the two VV centers with a V...V separation of 3.3275 (10) Å. Within the centrosymmetric edge-shared dioctahedral structure, each metal center is in a distorted octahedral NO5 environment, assembled by the O,N,O-donor L 2– ligand, bridging OMe− groups and the oxo group. The complex is diamagnetic in nature and brown in color. Solution electrical conductivity measurements confirmed its electrically non-conducting behavior.