Two oxidovanadium(V) complexes, [VOLLa] (1) and [VOLLb] (2), where L is the dianionic form of the Schiff base ligand 2-(((2-hydroxyethyl)imino)methyl)-6-methylphenol (H2L), La and Lb are the deprotonated forms of 3-hydroxy-2-methyl-4H-pyran-4-one (HLa) and 2-ethyl-3-hydroxy-4H-pyran-4-one (HLb), respectively, have been prepared and characterized by elemental analyses, IR, UV-Vis, 1H NMR and single-crystal X-ray crystallographic determination. The V atoms in the complexes are in octahedral coordination, with the Schiff base ligand mer-coordinated to the metal atoms through the phenolate O, imino N and hydroxyl O atoms, and with the pyrone ligands coordinated to the metal atoms through the two O atoms. The effect of the compounds on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans was studied.