The first two complexes of dioxovanadium(V) with salicylaldehyde thiosemicarbazone (SALTSC), of the coordination formulas [VO 2 (SALTSC– –H)]·H 2 O (1) and NH 4 [VO 2 (SALTSC–2H] (2), were synthesized and charac-terized by elemental analysis, conductometric measurements, IR and UV–Vis spectroscopy and X-ray analysis. The complexes were obtained in the reaction of an aqueous ammoniacal solution of NH 4 VO 3 and SALTSC. The results of the characterization showed that SALTSC was coordinated in the usual ONS tridentate mode as monoanion in complex 1 and dianion in complex 2. In both complexes, the vanadium atom is in a deformed square-pyramidal environment and is slightly shifted towards the apical oxo-ligand (≈ 0.52 Å).