A pair of oxidovanadium(V) complexes, [VOLL1] (1) and [VOLL2] (2), where L is the dianionic form of the hydrazone ligand N'-(5-chloro-2-hydroxybenzylidene)pivalohydrazide (H2L), L1 and L2 are the deprotonated forms of 3-hydroxy-2-methyl-4H-pyran-4-one (HL1; maltol) and 2-ethyl-3-hydroxy-4H-pyran-4-one (HL2; ethyl maltol), respectively, have been prepared and characterized by elemental analyses, IR and UV-Vis spectroscopy, and single-crystal X-ray crystallographic determination. The V atoms in the complexes are in octahedral coordination, with the hydrazone ligand coordinated to the V atoms through the phenolate O, imino N and enolate O atoms, and with the pyrone ligands coordinated to the V atoms through two O atoms. The effect of the compounds on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans was studied.