Abstract Solution equilibrium studies on the interaction of oxovanadium (IV) with iminodiacetic (IMDA) and nitrilotriacetic (NTA) acids have been carried out. pH‐Titrations of the reaction mixtures containing vanadyl sulphate and aminopolycarboxylic acid in equimolar ratio have shown the formation of 1:1 chelates. With IMDA, the possibility of 1:2 chelate (metal ion: IMDA) is also indicated. The equilibrium, chelate formation, hydrolysis and polymerization constants have been calculated at 25 and 30°C and also the thermodynamic functions viz. ΔH, ΔF, and ΔS.