The interaction of the vanadyl (IV) (VO2+) cation with carnosine (the dipeptide beta-alanyl-histidine) has been investigated by electron absorption spectroscopy at high ligand-to-metal ratios and at different pH values. The results show that in the range 6.0-8.5, the cation interacts with the imidazole group of four different carnosine molecules and points to the presence of an axially coordinated water molecule. These suppositions were confirmed by the behavior of the VO2+/imidazole system, which was investigated under similar experimental conditions, and supported by previous ENDOR (electron-nuclear double resonance) results. The study was complemented with additional measurements using the glycylglycine, glycylglycine/imidazole, and histidine systems as ligands.