The oxovanadium (IV) complexes of the hydrazones derived from 2-benzimidazolyl mercaptoaceto hydrazide and ohydroxy aromatic aldehydes have been described. These complexes have been characterized by elemental analyses, molar conductance, magnetic susceptibilities, Infrared, EPR and electronic spectral measurements. The IR spectra suggest the presence of phenoxide bridging and the complexes are formulated as dimers, each unit having five coordinate distorted square pyramidal geometry. The electronic spectra have been interpreted interms of energy level scheme delineated for distorted square pyramidal geometry. The low m eff values have been attributed to antiferromagnetic exchange coupling and the principal path for spin coupling is direct s-metal–metal interaction. The EPR spectrum of the complex indicates a characteristic of dimers with spin–spin coupling between the two adjacent vanadium atoms. The thermal stabilities have been studied by TG and the kinetic parameters of these complexes are calculated using Coats –Red fern and MKN methods. The ligands and their oxovanadium (IV) complexes were screened for their antimicrobial activities.