Highly selective poly(vinyl chloride) (PVC) membrane electrodes based on oxovanadium(IV) complexes of heteromacrocycle compounds as new ionophores for iodide-selective electrodes (ISEs) were fabricated with a composition of PVC (28.1 wt%), plasticizers (69.3 wt%), ionophores (2.6 wt%) and cation excluders (15 mol% relative to the ionophore). The prepared electrode on oxovanadium(IV) tetraphenyl porphyrin with o-NPOE as the membrane solvent and TDDACl as the cation excluder was found to exhibit the best sensitivity over a wide concentration range of 5.0×10–7 to 2.1×10–2 M with a Nernstian response of –59.02 mV per decade and the highest ion-selectivity toward the I– ions over perchlorate ions (I–/ClO4– = 91).