The binuclear oxidovanadium(V) complex [{VO(L)}2(μ-O)(μ-H2O)]∙2CH3CN (1), where L2– is the dianion of the Schiff base 2-salicylaldehyde-2-hydroxybenzoylhydrazone, were prepared and characterized by elemental analysis, FTIR, 1H, 13C and 51V NMR. Furthermore, the crystal structure of the compound 1 was determined by single crystal X-ray diffractometry revealing a distorted octahedral O5N-coordination geometry around the V(V) acceptor centers. The vanadium ions are connected by the μ-O2– and the μ-H2O asymmetric bridges located in the edge between the two octahedrons which keeps a distance of 3.194 Å between the two vanadium centers. Crystal data for C32H28N6O10V2 (M =758.48 g/mol): orthorhombic, space group P212121 (no. 19), a = 12.9655(8) Å, b = 14.1902(9) Å, c = 18.4379(10) Å, V = 3392.3(4) Å3, Z = 4, T = 293(2) K, μ(MoKα) = 0.616 mm-1, Dcalc = 1.485 g/cm3, 18803 reflections measured (3.622° ≤ 2Θ ≤ 56.704°), 8263 unique (Rint = 0.0473, Rsigma = 0.1020) which were used in all calculations. The final R1 was 0.0509 (I > 2σ(I)) and wR2 was 0.1531 (all data). The (VO)2(μ-O)(μ-H2O) core in compound 1 represents a rare case and few examples of similar type have been structurally characterized.