Poly(vinyl chloride) based membranes of di-(2-ethylhexyl)phosphoric acid (DEHPA) and dibutyl(butyl)phosphonate (DBBP) have been prepared and investigated as VO2+-selective sensors. The membranes containing DEHPA/DBBP and sodium tetraphenylborate, an anion excluder, show near-Nernstian/Nernstian response in the concentration range ∼10−5–10−1 M. The sensors exhibit a fast response time and good selectivity for VO2+ over a number of other cations. Quantitative determination of vanadium in waste V2O5 catalyst has been achieved by these sensors and they have also been used as indicator electrodes for the determination of the end point in the potentiometric titration of VO2+ against EDTA.