In order to assess the role of the low molecular mass bioligands of blood serum in vanadium binding, a study was made of the interactions of the complexes formed in the VO(IV)–picolinic acid and VO(IV)–6-methylpicolinic acid systems with various low molecular mass constituents of blood serum, such as oxalate, lactate, citrate and phosphate. The speciation of VO(IV) in these ternary systems and also in the binary VO(IV)–picolinic acid and VO(IV)–6-methylpicolinic acid systems was studied by pH-potentiometry at 25 °C and at an ionic strength I =0.2 M (KCl). The binding modes of the complexes formed were determined by spectral (electronic absorption and EPR) methods. Picolinic acid and 6-methylpicolinic acid were found to form mono and bis complexes through the pyridine nitrogen and carboxylate oxygen, but the presence of the methyl group in 6-methylpicolinic acid surprisingly decreases the stability of its complexes significantly. The results obtained on the ternary systems reveal that mixed ligand complex formation is favoured in these systems, especially with citrate, and must therefore be taken into account in the speciation description of VO(IV) in blood serum.